CN101153228A - Multi-metal noumenon catalyzer for hydrodesulphurization of diesel oil, producing method and application of the same - Google Patents
Multi-metal noumenon catalyzer for hydrodesulphurization of diesel oil, producing method and application of the same Download PDFInfo
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Abstract
A polymetallic bulk catalyst for diesel oil hydrodesulfurization is provided. The particle diameter of the present invention is 10-100 nm, and the present invention consists of a species of VIII metal and two species of VIB metal, wherein, the mole ratio of the VIII metal and the VIB metal is 1:9-9:1, while the mole ratio of two species of VIB metal is 1:5-5:1. The preparation method is that: a) the basic carbonate of VIII metal is led to dissolve in solvent to form suspension liquid; b) two species of metal salts of the VIB metal are led to dissolve in the solvent, and surfactant is added into the solvent, stirred and heated to 50-250 DEG C; c) the suspension liquid in step a is added into the solvent in step b and led to react in reflux for 4-25 hours under 50-250 DEG C; d) the product obtained in step c is filtered, washed and dried to obtain target product. The catalyst of the present invention is used in the ultra-deep hydrodesulfurization of diesel oil and shows extremely high hydrodesulfurization activity. Under the same operating conditions, the activity of the present invention is 5.9 times as much as industrial reference agent.
Description
Technical field
The present invention relates to a kind of multi-metal body catalyst that is used for the diesel oil ultra-deep hydrodesulfuration.
The invention still further relates to the preparation of above-mentioned multi-metal body catalyst.
The invention still further relates to the application of above-mentioned multi-metal body catalyst.
Background technology
Along with the environmental legislation of increasingly stringent, require the sulphur content in the liquid fuel more and more lower, but high-sulfur crude oil increase year by year in the world wide, therefore develop well behaved diesel oil ultra-deep hydrodesulfuration catalyzer, become new problem highly visible.As everyone knows, too high as the sulphur content in the diesel oil, after its burning, can form oxysulfide (SO
x) cause acid rain and solid dust to pollute, but also can make the three-way catalyst of motor vehicle tail-gas purifying system produce irreversible poisoning.For this reason, each state has all issued strict diesel oil sulphur content standard, and China will carry out suitable Europe IV (＜50ppm) emission standard (big cities such as Beijing, Shanghai 2 years in advance) on July 1st, 2010.Therefore, press for the requirement that catalyzer that development has a high hydrodesulfurization activity satisfies the super deep hydrogenation of diesel oil.
At present, the essentially consist of the Hydrobon catalyst of industrial use is all very similar, promptly do catalyst adjuvant with VIII family metal Co or Ni, do the catalyst activity component with group vib metal M o or W, adopt activated alumina or pure aluminium silicate to do carrier, can also improve the performance of catalyzer by the various auxiliary agents of interpolation (as boron, titanium, phosphorus or silicon).General catalyzer commonly used has: Co-Mo/Al
2O
3, Ni-Mo-P/Al
2O
3, Ni-W-B/Al
2O
3, Ni-Co-Mo/Al
2O
3And Co-W/Al
2O
3Deng.But more and more higher along with diesel oil sulphur content standard, these activity of such catalysts can not satisfy the ultra-deep desulfurization needs, therefore press for a kind of catalyzer that can realize Ultra-deep Desulfurization of Diesel Fuels.Adjusting process operational condition and use novel reactor all need huge investment cost, by contrast, develop and a kind ofly can on traditional production device, carry out the new catalyst of ultra-deep hydrodesulfuration according to existing operational condition, it is a kind of more economic, more feasible method.
As everyone knows, because the catalytic effect of carrier itself is limited, it just increases catalytic effect by the contact area of augmenting response thing and carrier or the synergy between carrier and active ingredient, so the hydrodesulfurization activity of general supported catalyst is difficult to improve significantly again.And multi-metal body catalyst, i.e. many metals non-supported catalyst, because it has the various active component, and the active centre number will be greatly more than supported catalyst, so it is a kind of very high catalytic activity catalyst that has.Wherein, metal group becomes a kind of body catalyst of NiMoW, in recent document and patent report, has demonstrated high hydrodesulfurization reaction activity, has caused people's extensive concern.
United States Patent (USP) 6299760,6156695,6783663,6712955,6758963 etc. reported that all novel NiMoW body catalyst is synthetic and used, and the hydrodesulfurization activity of this novel catalyzer is other about three times of industrial reference agent.The building-up process of this catalyzer all is to be complexing agent with ammoniacal liquor, with reaction raw materials Ni
2+Complexing, through slow heat-processed, nickel ammine slowly decomposites Ni
2+Generate the NiMoW catalyst precursor with molybdenum, tungsten reaction in the solution,, form the NiMoW catalyzer again by roasting and sulfuration.The weak point of this kind synthetic method is, has used strong aqua in the building-up process, can pollute environment.
In addition, people such as G.Alonso-Nunez (Applied Catalysis A:General 304 (2006) 124-130) in the literature; Applied Catalysis A:General 302 (2006) 177-184); CatalysisLetters 99 (2005) 65-71) reported the method for using different material and multiple vulcanizing agent to synthesize the NiMoW catalyzer.They synthesize the catalyzer that obtains and have special button shape form, also can have higher surface area.But his used synthetic method more complicated, and raw material costliness, complex production process has increased catalyst production cost, is difficult to realize industrialization.
Chinese patent 1339985A also discloses a kind of method of synthetic NiMoW catalyzer, the contriver mainly is in the aqueous solution, by molybdenum, tungsten salt and basic carbonate nickel reactant, guarantee at least in the reaction process that the metal ingredient of part exists with solid-state form, finally obtain catalyzer by sulfuration.Because the raw material that this method is used part is basic nickel carbonate, it is water insoluble, and this qualitative response of building-up process is the replacement(metathesis)reaction between ion and the solid, so be difficult to the synthetic catalyst particle that obtains nano-scale.
Be not difficult to find that the synthetic method of existing body catalyst is deposited following insufficient place from existing coverage: the raw material that use (1) is unfriendly to environment; (2) the Preparation of Catalyst cost is higher; (3) catalyst particle is bigger, and activity is still waiting further raising.
Summary of the invention
The purpose of this invention is to provide a kind of multi-metal body catalyst that is used for diesel hydrogenation for removal sulphur.
Another purpose of the present invention provides a kind of preparation method who prepares above-mentioned multi-metal body catalyst.
For achieving the above object, multi-metal body catalyst provided by the invention, its particle diameter are 10-100nm, are made up of a kind of VIII family's metal and two kinds of group vib metals; Wherein, the mol ratio of VIII family metal and group vib metal is 1: 9-9: 1, and preferred mol ratio is 1: 6-6: 1, the mol ratio of recommendation is 1: 3-3: 1; And the mol ratio of two kinds of group vib metals is 1: 5-5: 1, and preferred mol ratio is 1: 3-3: 1, the mol ratio of recommendation is 1: 2-2: 1.
Described multi-metal body catalyst wherein, preferably consists of cobalt molybdenum tungsten or nickel molybdenum tungsten, recommends nickel molybdenum tungsten.
The method of the above-mentioned multi-metal body catalyst of preparation provided by the invention the steps include:
A) subcarbonate with VIII family metal is dissolved in the solvent, forms suspension liquid;
B) two kinds of metal-salts with group vib are dissolved in the solvent, and add tensio-active agent, are heated with stirring to 50-250 ℃;
C) suspension liquid with step a adds in the step b solution, in 50-250 ℃ of following back flow reaction 4-25 hour, preferred 8-25 of reaction times hour, recommends 16-25 hour;
The preferred 50-200 of temperature among step b and the step c ℃, recommend 50-120 ℃;
D) product filtration, washing, the drying that step c is obtained obtains target product;
In above-mentioned preparation, the subcarbonate of the VIII family metal that is adopted can be commercially available commodity, or according to document (" Chinese Chemicals complete works ", second edition, the first volume, Beijing, Chemical Industry Press, 1998, p.98) method in was synthetic, it is made into the reaction suspension liquid again; The subcarbonate of VIII family metal exists with solid-state form and reacts, and it has remained to distinctive laminate structure own in the final body catalyst product.
Described solvent is: water, dehydrated alcohol, propyl carbinol, primary isoamyl alcohol, glycerol, quadrol, ethylene glycol or their mixed solvent, preferably water, quadrol, primary isoamyl alcohol, glycerol, ethylene glycol or their mixed solvent are recommended water, primary isoamyl alcohol, glycerol, ethylene glycol or their mixed solvent.
Described tensio-active agent is cationic surfactant or nonionic surface active agent, comprise: cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, Triton X-100, Triton X-114 or their combination, palmityl trimethyl ammonium chloride, Triton X-100, TritonX-114 or their combination are recommended in preferred cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Triton X-100, TritonX-114 or their combination.
Described preparation method, wherein, the group vib metal-salt comprises: ammonium molybdate, ammonium tungstate, ammonium metawolframate, Sodium orthomolybdate or sodium wolframate, recommend ammonium molybdate, ammonium tungstate or ammonium metawolframate.
Multi-metal body catalyst provided by the invention can be applied in the reaction of diesel oil ultra-deep hydrodesulfuration, 280-400 ℃ of its temperature of reaction, and hydrogen pressure 1-20MPa, hydrogen to oil volume ratio are 50-1000, volume space velocity 0.1-10h
-1
Multi-metal body catalyst of the present invention is done following processing before reacting:
(i) in air atmosphere, in 350-550 ℃ of roasting;
(ii) grind, mix pinch, moulding;
(iii) on hydrogenating desulfurization fixation reaction bed, carry out the original position sulfuration with the mixed gas of sulfurous organic compound and hydrogen.
Multi-metal body catalyst of the present invention is compared with known technology, has following advantage:
1, the raw material cheap and simple of synthetic catalyst among the present invention, the building-up process easy handling, for environmental friendliness, catalyzer can suitability for industrialized production.
2, synthetic catalyzer of the present invention has the nanoscale size, characteristics such as higher degree of scatter, uniform particle size distribution; And final product may keep the subcarbonate laminate structure, thereby increased activity of such catalysts.
3, this catalyzer is used for showing high hydrodesulfurization activity among the ultra-deep hydrodesulfuration of diesel oil, and under same operational condition, its activity is 5.9 times of industrial reference agent.
Description of drawings
Fig. 1 is X ray (XRD) spectrogram of catalyzer among each embodiment.Can observe the characteristic peak of the corresponding sulfide of forming several metals of catalyzer by the XRD spectra of catalyzer among the embodiment, explanation all can be synthesized the NiMoW catalyzer in most polar solvents, and each characteristic peak is smoother, illustrate to add to have formed corresponding metal sulfide, and the particle of catalyzer is littler through sulfidation.On the other hand, it can also be seen that the use of opposed polarity solvent is bigger for the influence of catalyzer.
Fig. 2 is that the scanning electronic microscope (SEM) and the transmission electron microscope (TEM) of NiMoW catalyzer characterizes: (a) electron scanning micrograph of the NiMoW catalyzer after the sulfuration; (b) the transmission electron microscope photo of the NiMoW catalyzer after the sulfuration.Can observe catalyzer by the transmission electron microscope test is by big or small homogeneous, and the particle of high dispersing is formed, and has nano-scale; Further can also observe the spacing striped that significantly belongs to respective metal sulfide by the test of transmission electron microscope, and the catalyzer that process synthetic catalyzer of the present invention is reported in document is compared has shorter striped and the accumulation of crystal face striped still less, can infer that thus synthetic catalyzer of the present invention has higher activity.
Embodiment
In order to further specify the present invention, enumerate following embodiment, but it does not limit the defined invention scope of each accessory claim.Such as, the present invention proposes to prepare the multi-metal body catalyst with nano-scale that comprises a kind of VIII family's metal and two kinds of group vib metals according to experimental result, this VIII family metal can be Co, Ni, Fe etc., and the group vib metal then can be Cr, Mo, W etc.; For brevity, only enumerated the embodiment of NiMoW here, but do not meaned that remaining metal can not realize the present invention.
Embodiment 1
The preparation of NiMoW body catalyst among the present invention:
A, take by weighing ammonium molybdate and ammonium metawolframate, wherein Mo respectively
6+0.01mol, W
6+0.01mol, they are dissolved in 350ml water and ethylene glycol and the palmityl trimethyl ammonium chloride mixed solvent, form solution, and this solution is heated to temperature of reaction, constantly stir; Take by weighing basic nickel carbonate subsequently, contain Ni according to the preparation of " Chinese Chemicals complete works " disclosed method
2+0.03mol, it is dissolved in a spot of polar solvent, be made into suspension liquid, and be heated to temperature of reaction; This reaction suspension liquid is added in the colourless transparent solution at leisure, form the light green reaction solution, back flow reaction is 20 hours under 150 ℃ of temperature of reaction; Yellow-green colour powder filter, washing that reaction is obtained, and, obtain the NiMoW catalyst precursor 120 ℃ of oven dry.
B, the precursor with this catalyzer carries out roasting then, condition is that 400 ℃ of burnings (were carried out roasting to catalyst precursor in 2 hours in the air atmosphere, its objective is for exist in the burn off catalyst precursor can decomposes impurity, obtain the oxide form precursor of catalyzer), obtain NiMoW catalyst oxidation thing precursor.Before carrying out hydrogenating desulfurization and some signs, this catalyst precursor is being vulcanized, cure conditions is at 10%H
2S/H
2In the atmosphere, reacted 2 hours down at 400 ℃, wherein 10%H
2S/H
2Flow velocity be 60 ml/min, vulcanizing agent can be the mixed gas of hydrogen sulfide and hydrogen, also can be the mixed gas of other sulfurous organic compound and hydrogen.
The synthetic catalyzer is represented with Cat-A among this embodiment, and its XRD characterization result is listed among Fig. 1, and its transmission electron microscope, electron scanning micrograph are listed among Fig. 2.
Can observe catalyzer by the transmission electron microscope test is made up of the particle of 10-100nm.
This catalyzer is used for showing high hydrodesulfurization activity among the ultra-deep hydrodesulfuration of diesel oil, and under same operational condition, its activity is 5.9 times of industrial reference agent.
Embodiment 2
With embodiment 1, just only used polar solvent water and ethylene glycol among the step a, the synthetic catalyst product is represented with Cat-B.Its XRD characterization result is listed among Fig. 1.
Embodiment 3
With embodiment 1, just used polar solvent ethylene glycol among the step a, the synthetic catalyst product is represented with Cat-C.Its XRD characterization result is listed among Fig. 1.
Embodiment 4
With embodiment 1, just used the polar solvent primary isoamyl alcohol among the step a, the synthetic catalyst product is represented with Cat-D.Its XRD characterization result is listed among Fig. 1.
Embodiment 5
With embodiment 1, just used the polar solvent glycerol among the step a, the synthetic catalyst product is represented with Cat-E.Its XRD characterization result is listed among Fig. 1.
Embodiment 6
With embodiment 1, just used the commercial goods basic nickel carbonate to replace own synthetic basic nickel carbonate raw material among the step a, the synthetic catalyst product is represented with Cat-F.Its XRD characterization result is listed among Fig. 1.
Embodiment 7
With embodiment 1, just use ammonium molybdate and ammonium tungstate to be raw material among the step a, the synthetic catalyst product is represented with Cat-G.
Embodiment 8
With embodiment 1, just use Sodium orthomolybdate and sodium wolframate to be raw material among the step a, the synthetic catalyst product is represented with Cat-H.
Embodiment 9
With embodiment 1, just the feed ratio among the step a is Ni: Mo: W=1: 1: 2, the synthetic catalyst product was represented with Cat-I.
Embodiment 10
With embodiment 1, just the feed ratio among the step a is Ni: Mo: W=6: 2: 1, the synthetic catalyst product was represented with Cat-J.
Embodiment 11
With embodiment 1, just the polar solvent that uses among the step a is water, ethylene glycol and tensio-active agent Triton X-100, and the synthetic catalyst product is represented with Cat-K.
Embodiment 12
With embodiment 1, just the polar solvent that uses among the step a is water, ethylene glycol and tensio-active agent octadecyl trimethylammonium bromide, and the synthetic catalyst product is represented with Cat-L.
Embodiment 13
With embodiment 1, just the catalyzer synthesis reaction temperature is 90 ℃ among the step a, and the synthetic catalyzer is represented with Cat-M.
Embodiment 14
With embodiment 1, just the catalyzer synthesis reaction temperature is 50 ℃ among the step a, and the synthetic catalyzer is represented with Cat-N.
Embodiment 15
With embodiment 1, just the catalyzer synthesising reacting time is 4 hours among the step a, and the synthetic catalyzer is represented with Cat-O.
Embodiment 16
The research of NiMoW catalyzer performance in hydrodesulfurization reaction
The true diesel oil that with the sulphur content is 1200ppm is investigated the performance of NiMoW catalyzer in hydrodesulfurization reaction, is reflected in the fixed-bed reactor and carries out.Reaction conditions is: catalyst n iMoW quality 1g, and temperature of reaction is at 300 ℃, and hydrogen pressure 3.5Mpa, hydrogen-oil ratio are 600, volume space velocity 6h
-1What adopt for the test of sulphur content in the sample is the micro-coulometric titration instrument.
The activity of Cat-A, Cat-B, Cat-C, Cat-D, Cat-E, Cat-F, Cat-G, Cat-H, Cat-I, Cat-J and industrial reference agent has been compared in the performance test test, and the results are shown in Table 1 for reactive behavior.
The comparison of table 1, several NiMoW catalyzer and industrial reference agent hydrodesulfurization activity
| Catalyzer | Desulphurizing activated relatively | Catalyzer | Desulphurizing activated relatively |
| Cat-A | 551 | Cat-H | 239 |
| Cat-B | 320 | Cat-I | 194 |
| Cat-C | 347 | Cat-J | 314 |
| Cat-D | 358 | Cat-K | 483 |
| Cat-E | 303 | Cat-L | 502 |
| Cat-F | 185 | Cat-M | 431 |
| Cat-G | 593 | Cat-N | 218 |
| Well-known catalysts | 100 | Cat-O | 103 |
The present invention prepares activity of such catalysts and represents with relative reactivity, is 100 with 200 hours activity of reference agent running promptly, catalyzer of the present invention with it relatively the activity of gained represent the relative reactivity of invention catalyzer.Desulphurizing activated relatively by following formula calculating:
Desulphurizing activated relatively=100 * [(1/S
p)
1/2-(1/S
f)
1/2]/[(1/S
Pr)
1/2-(1/S
Fr)
1/2]
In the formula: S
Fr, S
PrRepresent the raw materials used oil of reference agent respectively and contain sulphur concentration, S through reference agent hydrotreatment after product
f, S
pRepresent that respectively raw materials used oil of invention catalyzer and the product after the invention catalyst hydrogenation is handled contain sulphur concentration.
Data by table 1 relatively can sum up certain law: in the dissimilar polarity solvent, the synthetic NiMoW catalyst hydrodesulfurization active that obtains has very big difference; By the specific activity between Cat-A and the Cat-B, can see that the adding of synthetic middle tensio-active agent has improved activity of such catalysts; By active comparison between Cat-A and the Cat-F, as can be seen, use different Ni sources, for catalyst activity very big influence is arranged also; By the change of other preparation conditions, activity of such catalysts all there are some influences; In addition, by NiMoW catalyzer and well-known catalysts hydrodesulfurization activity more as can be seen, the catalytic activity of the NiMoW body catalyst of the present invention preparation is far longer than well-known catalysts.
In sum, the present invention prepares the solvent composition of catalyzer by modulation optimization, use homemade Ni source, synthesized multi-metal body catalyst with higher hydrodesulfurization activity, this catalyzer has nanoscale, higher degree of scatter, uniformly characteristics such as particle size distribution, and its activity will be far longer than commercial catalysts, demonstrate huge industrial application value.
Claims (10)
1. multi-metal body catalyst that is used for diesel hydrogenation for removal sulphur, its particle diameter is 10-100nm, is made up of a kind of VIII family's metal and two kinds of group vib metals; Wherein, the mol ratio of VIII family metal and group vib metal is 1: 9-9: 1; And the mol ratio of two kinds of group vib metals is 1: 5-5: 1.
2. multi-metal body catalyst as claimed in claim 1, wherein, the mol ratio of VIII family metal and group vib metal is 1: 6-6: 1, preferably 1: 3-3: 1.
3. multi-metal body catalyst as claimed in claim 1, wherein, the mol ratio of two kinds of group vib metals is 1: 3-3: 1, preferably 1: 2-2: 1.
4. multi-metal body catalyst as claimed in claim 1, wherein, it consists of cobalt molybdenum tungsten or nickel molybdenum tungsten.
5. a method for preparing the described multi-metal body catalyst of claim 1 the steps include:
A) subcarbonate with VIII family metal is dissolved in the solvent, forms suspension liquid;
B) two kinds of metal-salts with group vib are dissolved in the solvent, and add tensio-active agent, are heated with stirring to 50-250 ℃;
C) suspension liquid with step a adds in the step b solution, in 50-250 ℃ of following back flow reaction 4-25 hour;
D) product filtration, washing, the drying that step c is obtained obtains target product;
Described solvent is: water, dehydrated alcohol, propyl carbinol, primary isoamyl alcohol, glycerol, quadrol, ethylene glycol or their mixed solvent;
Described tensio-active agent is: cationic surfactant or nonionic surface active agent.
6. preparation method as claimed in claim 5 is characterized in that, described group vib metal-salt comprises: ammonium molybdate, ammonium tungstate, ammonium metawolframate, Sodium orthomolybdate or sodium wolframate.
7. preparation method as claimed in claim 5, wherein, described solvent is: water, primary isoamyl alcohol, glycerol, ethylene glycol or their mixed solvent.
8. preparation method as claimed in claim 5, wherein, described tensio-active agent is: cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, Triton X-100 or Triton X-114 or their combination.
9. the application of the described multi-metal body catalyst of claim 1 in the diesel hydrogenation for removal sulphur reaction, temperature of reaction 280-400 ℃, hydrogen pressure 1-20MPa, hydrogen to oil volume ratio are 50-1000, volume space velocity 0.1-10h
-1
10. application as claimed in claim 9, wherein, before reacting multi-metal body catalyst is done following processing:
(i) in air atmosphere, in 350-550 ℃ of roasting;
(ii) grind, mix pinch, moulding;
(iii) on hydrogenating desulfurization fixation reaction bed, carry out the original position sulfuration with the mixed gas of sulfurous organic compound and hydrogen.
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| WO2011075928A1 (en) * | 2009-12-23 | 2011-06-30 | 中国科学院大连化学物理研究所 | Multi-metal bulk catalyst with layered structure and preparation method and use thereof |
| CN101664682B (en) * | 2008-09-05 | 2011-12-28 | 中国石油化工股份有限公司 | Non-noble metal supported selective hydrogenation catalyst and preparation method and application thereof |
| WO2014043993A1 (en) * | 2012-09-18 | 2014-03-27 | 中国科学院大连化学物理研究所 | Preparation and application of ultra-deep hydrodesulfurization multi-metal bulk catalyst of layered structure |
| CN105312060A (en) * | 2014-07-17 | 2016-02-10 | 中国科学院大连化学物理研究所 | Multi-metal body catalyst with layered structure, preparation and applications thereof |
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| WO2011075928A1 (en) * | 2009-12-23 | 2011-06-30 | 中国科学院大连化学物理研究所 | Multi-metal bulk catalyst with layered structure and preparation method and use thereof |
| CN101733120B (en) * | 2009-12-23 | 2012-11-21 | 中国科学院大连化学物理研究所 | Multi-metal body catalyst with laminated structure, preparation method and application thereof |
| US9457342B2 (en) | 2009-12-23 | 2016-10-04 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Multi-metallic bulk catalyst with layered structure and method for the preparation and use thereof |
| US9669392B2 (en) | 2012-08-30 | 2017-06-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for selective hydrogenation of dienes, preparation method and application thereof |
| WO2014043993A1 (en) * | 2012-09-18 | 2014-03-27 | 中国科学院大连化学物理研究所 | Preparation and application of ultra-deep hydrodesulfurization multi-metal bulk catalyst of layered structure |
| CN105312060A (en) * | 2014-07-17 | 2016-02-10 | 中国科学院大连化学物理研究所 | Multi-metal body catalyst with layered structure, preparation and applications thereof |
| CN106311259A (en) * | 2015-06-25 | 2017-01-11 | 中国科学院大连化学物理研究所 | Gasoline selective hydrodesulfurization bulk phase catalyst, and preparation method and application thereof |
| CN106311259B (en) * | 2015-06-25 | 2019-02-19 | 中国科学院大连化学物理研究所 | A kind of gasoline selective hydrodesulfurizationmodification bulk phase catalyst and its preparation method and application |
| CN106994350A (en) * | 2016-01-22 | 2017-08-01 | 中国科学院大连化学物理研究所 | A kind of gasoline selective hydrodesulfurizationmodification bulk phase catalyst and its preparation and application |
| CN106622299A (en) * | 2016-12-10 | 2017-05-10 | 辽宁石油化工大学 | Preparation method of high-HDS-activity Ni-based non-loading type catalyst |
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