CN1840617A - Sulfide catalyst for hydrogenation desulfurization and denitrogenation and its preparation process and use - Google Patents
Sulfide catalyst for hydrogenation desulfurization and denitrogenation and its preparation process and use Download PDFInfo
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- CN1840617A CN1840617A CN 200510062483 CN200510062483A CN1840617A CN 1840617 A CN1840617 A CN 1840617A CN 200510062483 CN200510062483 CN 200510062483 CN 200510062483 A CN200510062483 A CN 200510062483A CN 1840617 A CN1840617 A CN 1840617A
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Abstract
The preparation method for HDSN sulfide catalyst comprises: mixing element precursor from VIB and VIII family with S-contained precursor, adding reducer to produce the sulfide contained VIB and VIII elements at given temperature; separating nano particle from reaction system, drying, and hot processing in inert/sulfidization atmosphere. This product has activity 4-5 times than the industrial product.
Description
Technical field
The present invention relates to a kind of super-active hydrogenating desulfurization nanometer sulfide catalyzer.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to above-mentioned Application of Catalyst.
Background technology
The oil fuel ultra-deep desulfurization has become the global range important research project to be solved of having to go to the toilet.Countries such as America and Europe have worked out strict more environmental legislation, execution are lower than the ultra-low-sulphur diesel standard of 15ppm before 2006.Yet, utilize existing Hydrobon catalyst to be difficult to the sulphur in the diesel oil is taken off to the super low sulfur level that is lower than 15ppm.At present, carrying out a large amount of research work aspect the existing Hydrobon catalyst activity of improvement, mainly concentrating on and use new carrier, add new active ingredient or auxiliary agent, optimization sulfidation, use different activities component (molybdenum, tungsten) precursor and develop new preparation method or the like.
At present, carried out a large amount of basic research works aspect hydrogenating desulfurization, a kind of generally accepted viewpoint is: the active centre of sulfide catalyst is positioned at Mo (W) S
2The limit face of small pieces, these small pieces are short more, and the limit face is just many more, thereby activity of such catalysts is just high more.Yet, with Mo (W) S of traditional Hydrobon catalyst of wet method preparation
2Small pieces are relatively large, so only there is the small part active centre to obtain utilizing in existing Hydrobon catalyst.The active method of a possible raising Hydrobon catalyst is the nanophase molybdenum base or the tungsten-based catalyst of synthetic high dispersing.
Synthetic nanophase molybdenum base or the tungsten sill that does not contain auxiliary agent adopts usually: high temperature vulcanized, solvent thermal reaction of thermolysis sulphur ammonium molybdate, ultrasonic synthetic, molybdenum oxide or Tungsten oxide 99.999 or the like.At present, about being that the synthetic of the molybdenum base of auxiliary agent or tungsten base nanometer sulfide catalyzer still do not have patent report with group VIII metal (iron, cobalt, nickel, ruthenium etc.), has only odd bibliographical information.As people such as Suslick (J.Am.Chem.Soc.2001,123,6310-8316.) introduced the synthetic CoMoS/Al with nanophase structure of ultrasonic method
2O
3, NiMoS/Al
2O
3And CoNiMoS/Al
2O
3Hydrobon catalyst.The synthetic method that they adopt is: containing in the reaction box of rare gas element, with SULPHUR POWDER and 1,2,3,5-tetramethyl-benzene organic solvent mixes, and after ultrasonic, adds a certain amount of Mo (CO)
6, Co (CO)
6And γ-Al
2O
3, with the reaction vessel sealing, in reaction box, take out then, ultrasonic 1.5 hours in 80 ℃ under the argon shield of flowing.The slurry of the black that obtains is filtered out in inert atmosphere, with the pentane washing several times, through the powder of washing in a vacuum in 80 ℃ of solvents of removing unreacted precursor and absorption, at last at 450 ℃ mobile 10%H
2Handle 10 hours in the/He mixed gas to remove excessive SULPHUR POWDER, obtain CoMoS/Al
2O
3Catalyzer.NiMoS/Al
2O
3Catalyzer adopts similar method preparation, and different is that used Ni precursor uses network and thing Ni (N
2H
5) (N
2H
3COO)
3H
2O.They are used for the hydrogenating desulfurization of model molecule thiophene and dibenzothiophene with the catalyzer that makes, find nanophase activity of such catalysts (TOF) be commercial catalysts 1-2 doubly.
People (Applied Catalysis A:General258 (2004) 83-91.) such as the Marshall of U.S. Argonne National Laboratory use similar method to synthesize the unsupported CoMoS catalyzer with nanophase structure, and the method that they use is: with Mo (CO)
6, Co
2(CO)
8And SULPHUR POWDER joins in the n-Hexadecane solvent, and under nitrogen protection, supersound process 40 hours has obtained the catalyzer of nanophase structure.They compare nanometer sulfide catalyzer and the commercial catalysts that makes, and find that the nanometer sulfide activity of such catalysts is approximately higher than commercial catalysts.
Be not difficult to find that the synthetic method of existing nanometer sulfide catalyzer also has the following improved place for the treatment of from above two pieces of document analysises: (1) uses deleterious carbonyl compound as active ingredient and auxiliary agent precursor, and is unfriendly to environment; (2) the synthetic cost height of catalyzer; (3) ultrasonic procedure is not easy to realize heavy industrialization; (4) poor heat stability of Zhi Bei nanometer sulfide catalyzer; (5) catalyst activity is still waiting further raising; (6) use thiophene and dibenzothiophene can not represent the character of true diesel oil as the model molecule, because the most difficult sulfur-containing molecules that removes is 4 in the diesel oil, the 6-dimethyl Dibenzothiophene; (7) repercussion study that nanometer sulfide is used for hydrodenitrification does not appear in the newspapers as yet.
Summary of the invention
The object of the present invention is to provide a kind of hydrogenation desulfurization and denitrogenation nanometer sulfide catalyzer.
Another purpose of the present invention is to provide above-mentioned Preparation of catalysts method.
For achieving the above object, catalyzer provided by the invention is the sulfide particles of group vib, group VIII element, the mol ratio of group VIII and group vib element is 0.01-0.99, is preferably 0.10-0.70, and the sulfide of group VIII element is dispersed on the sulfide of group vib element; The size of catalyst particle in 1 nanometer to 1000 nanometer range, preferred size in 1 nanometer to 50 nanometer range, 5 nanometer to 20 nanometers preferably.
The method of the above-mentioned catalyzer of preparation provided by the invention is as follows:
Behind group vib element precursor, group VIII element precursor and sulfur-bearing precursor thorough mixing, add reductive agent, under certain temperature of reaction, group vib element and group VIII element form the nanometer sulfide particle with homogeneous phase, these nanoparticles are separated from reaction system, promptly obtained the nanometer sulfide catalyzer after drying, inert atmosphere or the vulcanized gas pyroprocessing.Above-mentioned nanometer sulfide catalyzer is squeezed into definite shape is used for hydrodesulfurization reaction under the situation that adds or do not add carrier, can with contain in the diesel oil 4, nitrogen in sulphur in the 6-dimethyl Dibenzothiophene and the nitrogenous organic molecule takes off to super low sulfur and ultralow nitrogen level (being lower than 15ppm), thereby realizes the ultra-deep desulfurization process of diesel oil.
Group vib element of the present invention is meant chromium, molybdenum, tungsten and/or their combination, preferred molybdenum, tungsten and/or their combination; Specifically, group vib element precursor is meant the compound that contains the group vib element, can be oxide-based, acids, salt and/or their combination; More specifically, said group vib element precursor is meant molybdenum oxide, Tungsten oxide 99.999 and/or their combination, acids is meant molybdic acid, wolframic acid and/or their combination, salt is meant molybdate, sulphur molybdate, tungstate, sulphur tungstate and/or their combination, preferred molybdic acid, wolframic acid, ammonium molybdate, ammonium tungstate, sulphur ammonium molybdate, sulphur ammonium tungstate and/or their combination, preferably sulphur ammonium molybdate, sulphur ammonium tungstate and/or their combination;
Group VIII element of the present invention is meant iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and/or their combination, preferred iron, cobalt, nickel and/or their combination, preferably cobalt, nickel and/or their combination; Specifically, group VIII element precursor is meant the compound that contains the group VIII element, can be oxide-based, bases, salt and/or their combination; More particularly, the precursor of group VIII element is meant ferric oxide, ironic hydroxide, iron nitrate, ferric sulfate, iron(ic) chloride, ferrous ammonium sulphate, iron carbonate, iron acetate, ironic oxalate, cobalt oxide, cobaltous hydroxide, Xiao Suangu, rose vitriol, cobalt chloride, cobaltous dihydroxycarbonate, Cobaltous diacetate, cobalt oxalate, nickel oxide, nickel hydroxide, nickelous nitrate, single nickel salt, nickelous chloride, basic nickel carbonate, nickel acetate, nickelous oxalate and/or their combination; Preferred iron nitrate, Xiao Suangu, nickelous nitrate, iron acetate, Cobaltous diacetate, nickel acetate, ironic oxalate, cobalt oxalate, nickelous oxalate and/or their combination; Preferably iron acetate, Cobaltous diacetate, nickel acetate and/or their combination.
Sulfur-bearing precursor of the present invention is meant S
8And/or can produce S by chemical reaction
8The sulfur-bearing precursor, contain S
2-Sulfide and/or can produce S by chemical reaction
2-Sulfur-bearing precursor, polysulfide and/or can produce the precursor of polysulfide and/or their combination, preferred thiocarbamide, (NH by chemical reaction
4)
2S, (NH
4)
2S
x(x＞1), S
8And/or their combination, preferably S
8
Reductive agent of the present invention is meant the organic molecule that contains oh group (OH), the carboxylic-acid that preferably contains a plurality of hydroxyls, contain the polyprotonic acid and its esters of a plurality of carboxyls and contain the polyalcohols organic molecule of a plurality of hydroxyls and/or their combination, the polycarboxylic acid class that preferably contains a plurality of hydroxyls, polynary hydrochlorate, contain the di-alcohols of two hydroxyls and/or their combination, specifically, they can be oxalic acid, citric acid, ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), ammonium oxalate, ammonium citrate, the ethylenediamine tetraacetic acid (EDTA) ammonium, the nitrilotriacetic acid(NTA) ammonium, ethylene glycol, glycerol, the dihydroxyl propyl alcohol, dihydroxyl butanols and/or their combination, preferred ethylenediamine tetraacetic acid (EDTA) and/or ethylenediamine tetraacetic acid (EDTA) ammonium, ethylene glycol and/or their combination.
Preparation of Catalyst temperature of reaction of the present invention is meant from room temperature to 300 ℃, preferred 100 ℃ to 250 ℃, and best 120 ℃ to 210 ℃.
Group vib element of the present invention is meant with the elementary composition sulfide particles with nanoscale of group VIII and only observes on the X-ray diffractogram and the relevant diffraction peak of group vib element sulfide, and diffraction peak does not appear in the sulfide of group VIII element, and the sulfide high dispersing of group VIII element is on the sulfide of group vib element.
Inert atmosphere of the present invention is meant not the gas that reacts with the nanometer sulfide catalyzer, comprises nitrogen, helium, neon, argon gas and/or their combination, preferred nitrogen, argon gas and/or their combination, preferably nitrogen.Described vulcanized gas is meant the mixed gas of hydrogen and hydrogen sulfide.
Nanometer sulfide catalyzer provided by the invention, the application conditions in hydrogenating desulfurization is: 280 ℃-340 ℃ of temperature, liquid hourly space velocity is 0.5-30h
-1, hydrogen pressure is 2-10MPa, hydrogen to oil volume ratio is to react under the reaction conditions of 150-600.The result shows that the 4-5 that this nanometer sulfide activity of such catalysts is a commercial catalysts doubly.
Specifically, compared with prior art, superelevation hydrodesulfurization activity nanometer sulfide Catalysts and its preparation method of the present invention has the following advantages:
1) use nontoxic active ingredient and auxiliary agent as precursor, environmentally friendly;
2) process for synthetic catalyst is simple relatively, thereby synthetic cost is relatively low;
3) be easy to heavy industrialization;
The thermostability of the nanometer sulfide catalyzer that 4) makes is higher;
5) activity of such catalysts is greatly improved;
6) use 4, the 6-dimethyl Dibenzothiophene has been carried out hydrodesulfurization activity relatively as the model molecule to nanometer sulfide catalyzer and the commercial catalysts that makes, and the result is more convincing;
7) catalyzer has high hydrodenitrogenationactivity activity, the hydrogenating desulfurization of producing according to present method, the activity of denitrification catalyst be industrial reference catalyst 4-5 doubly.
Embodiment
In order to further specify the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1
Nanometer NiMoS Preparation of catalysts.
As an illustrative examples, nanometer NiMoS catalyzer can prepare as follows: with 2.466 gram Ammonium Heptamolybdates, 2.000 gram b diammonium edtas, 2.630 gram nickelous nitrates, 1.000 gram S
8Join in 60 milliliters of ethylene glycol solutions, the slurry of formation is warmed up to 120 ℃ under nitrogen protection and vigorous stirring, and keeps 10 hours under this temperature, and the black precipitate that obtains promptly obtains the nanometer sulfide catalyst A through washing, drying and sulfidizing.
Embodiment 2
With embodiment 1, just temperature of reaction is 150 ℃, and the nanometer sulfide catalyzer that obtains is labeled as B.
Embodiment 3
With embodiment 1, just temperature of reaction is 210 ℃, and the nanometer sulfide catalyzer that obtains is labeled as C.
Embodiment 4
With embodiment 1, just b diammonium edta is changed into 2.000 gram nitrilotriacetic acid(NTA)s, temperature of reaction is a room temperature, the nanometer sulfide catalyzer that obtains is labeled as D.
Embodiment 5
With embodiment 1, just nickelous nitrate is changed into 2.630 gram nickel acetates, temperature of reaction is 300 ℃, the nanometer sulfide catalyzer that obtains is labeled as E.
Embodiment 6
With embodiment 1, just Ammonium Heptamolybdate is changed into 2.000 gram sulphur ammonium molybdates, the nanometer sulfide catalyzer that obtains is labeled as F.
Embodiment 7
With embodiment 6, just the sulphur ammonium molybdate is changed into 2.000 gram sulphur ammonium tungstates, the nanometer sulfide catalyzer that obtains is labeled as G.
Embodiment 8
With embodiment 1, just in reaction system, add 1.000 gram γ-Al
2O
3, the nanometer sulfide catalyzer that obtains is labeled as H.
Embodiment 9
With embodiment 3, just nickelous nitrate is changed into the mixture of 1.200 gram Xiao Suangus and 1.400 gram nickelous nitrates, the nanometer sulfide catalyzer that obtains is labeled as I.
Embodiment 10
With embodiment 6, just the sulphur ammonium molybdate is changed into the mixture of 1.000 gram sulphur ammonium tungstates and 1.000 gram sulphur ammonium molybdates, the nanometer sulfide catalyzer that obtains is labeled as J.
Embodiment 11
With embodiment 6, just nickelous nitrate is changed into 1.200 gram ruthenium trichlorides, the nanometer sulfide catalyzer that obtains is labeled as K.
Embodiment 12
With embodiment 11, just in reaction system, add 1.000 gram γ-Al
2O
3, the nanometer sulfide catalyzer that obtains is labeled as L.
Embodiment 13
With embodiment 6, just in reaction system, add 1.000 gram γ-Al
2O
3, the nanometer sulfide catalyzer that obtains is labeled as M.
Embodiment 14
With embodiment 9, just in reaction system, add 1.000 gram γ-Al
2O
3, the nanometer sulfide catalyzer that obtains is labeled as N.
Embodiment 15
With embodiment 9, just in the nanometer sulfide powder that obtains, add 1.000 gram γ-Al
2O
3, compression molding behind the thorough mixing, the nanometer sulfide catalyzer that obtains is labeled as O.
Embodiment 16
With embodiment 3, just nickelous nitrate is changed into 3.000 gram ferrous ammonium sulphates, the nanometer sulfide catalyzer that obtains is labeled as P.
Embodiment 17
With embodiment 1, just Ammonium Heptamolybdate is changed into 2.5 gram molybdenum oxides, the nanometer sulfide catalyzer that obtains is labeled as Q.
Embodiment 18
With embodiment 1, just with S
8Change 7.000 milliliter of 50% ammonium sulfide solution into, the nanometer sulfide catalyzer that obtains is labeled as R.
Embodiment 19
With embodiment 6, just the volume with ethylene glycol changes 45 milliliters into, and the nanometer sulfide catalyzer that obtains is labeled as S.
Embodiment 20
With embodiment 6, just the volume with ethylene glycol changes 80 milliliters into, and the nanometer sulfide catalyzer that obtains is labeled as T.
Embodiment 21
With embodiment 6, just the volume with ethylene glycol changes 120 milliliters into, and the nanometer sulfide catalyzer that obtains is labeled as U.
The application of embodiment 22 catalyzer in diesel oil hydrofining
As hydrogenating desulfurization and denitrogenation experiment, commercial catalysts RN-1 is as the contrast experiment with catalyst A～R.(A～R) and commercial catalysts (RN-1) operation condition are identical for the catalyzer of preparation.Get in catalyzer 1.000 gram (20～40 order) micro fixed-bed reactors of packing into, reduce to 200 ℃ after 2 hours 400 ℃ of prevulcanizeds, feed and contain 4, the model diesel oil of 6-dimethyl Dibenzothiophene and pyridine (sulphur content 1000 μ g/g, total nitrogen content is 1000 μ g/g, and naphthane is a solvent).Being warming up to 340 ℃, is 2h in air speed
-1, the hydrogen dividing potential drop is 5MPa, hydrogen-oil ratio (volume) is to react under 400 the condition.
The activity of catalyst A～R of the present invention is represented with relative reactivity, is 100 with 30 hours activity of contrast commercial catalysts RN-1 running promptly, and the activity that catalyst A～R of the present invention obtains is by comparison represented 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]
S in the formula
Fr, S
PrThat represents raw materials used oil of reference catalyst RN-1 and the product after reference catalyst is handled respectively contains sulphur concentration, S
f, S
pRepresent respectively the invention catalyzer (the raw materials used oil of A～R) and through the invention catalyzer (product after the hydrotreatment of A～R) contain sulphur concentration.
Denitrification activity calculates by following formula relatively:
Relative denitrification activity=100ln (N
f/ N
p)/ln (N
Fr/ N
Pr)
N in the formula
Fr, N
PrThat represents the raw materials used and product after the reference catalyst hydrotreatment of reference catalyst RN-1 respectively contains nitrogen concentration, N
f, N
pRepresent respectively the invention catalyzer (the raw materials used oil of A～R) and through the invention catalyzer (product after the hydrotreatment of A～R) contain nitrogen concentration.
Active comparing result is as shown in table 1.
The active comparing result of table 1
| Catalyzer | Reaction times (hour) | Relative denitrification activity | Desulphurizing activated relatively |
| A | 30 | 405 | 418 |
| B | 30 | 420 | 435 |
| C | 30 | 460 | 480 |
| D | 30 | 435 | 429 |
| E | 30 | 467 | 478 |
| F | 30 | 484 | 491 |
| G | 30 | 436 | 447 |
| H | 30 | 447 | 465 |
| I | 30 | 459 | 480 |
| J | 30 | 492 | 500 |
| K | 30 | 408 | 426 |
| L | 30 | 417 | 434 |
| M | 30 | 402 | 413 |
| N | 30 | 424 | 437 |
| O | 30 | 457 | 467 |
| P | 30 | 484 | 498 |
| Q | 30 | 454 | 478 |
| R | 30 | 408 | 425 |
| S | 30 | 456 | 438 |
| T | 30 | 498 | 475 |
| U | 30 | 497 | 480 |
The 4-5 that is industrial reference catalyst according to the desulfurization and the denitrification activity of the prepared catalyzer of the present invention doubly, illustrate that catalyzer of the present invention has superelevation hydrogenating desulfurization and denitrification activity, can with in the diesel oil the most difficult remove 4, sulphur in the 6-dimethyl Dibenzothiophene and the nitrogen effective elimination in the pyridine.Thereby catalyzer of the present invention is particularly suitable for production super low sulfur, low nitrogen diesel oil (being lower than 15ppm).
Claims (13)
1. hydrodesulfurization activity sulfide catalyst, it is the sulfide particles of group vib, group VIII element, wherein the mol ratio of group VIII and group vib element is 0.01-0.99, and the sulfide of group VIII element is dispersed on the sulfide of group vib element; The size of catalyst particle is in 1 nanometer to 1000 nanometer range; The mol ratio of sulphur and total metal is 1.00-6.00 in the catalyzer.
2. the catalyzer of claim 1 is characterized in that, the mol ratio of group VIII and group vib element is 0.10-0.70.
3. the catalyzer of claim 1 is characterized in that, the size of catalyst particle is in 5 nanometer to 20 nanometer range.
4. the catalyzer of claim 1 is characterized in that, the mol ratio of sulphur and total metal is 2-4 in the catalyzer.
5. the method for preparing the described catalyzer of claim 1, main process is:
With group vib element precursor, group VIII element precursor, sulfur-bearing precursor and reductive agent, the weight ratio of reductive agent and each precursor sum is 5.50-15.50; Mix the formation slurry, temperature of reaction is a room temperature to 300 ℃, and protection of inert gas reaction 6-12 hour is down filtered, washing, after the drying precipitate in the mixed gas of hydrogen and hydrogen sulfide sulfidizing, obtain target product;
Described group vib element precursor is meant molybdenum oxide, Tungsten oxide 99.999 and/or their combination; Molybdic acid, wolframic acid and/or their combination; Molybdate, sulphur molybdate, tungstate, sulphur tungstate and/or their combination;
Described group VIII element precursor is meant ironic hydroxide, iron nitrate, ferric sulfate, iron(ic) chloride, ferrous ammonium sulphate, iron carbonate, iron acetate, ironic oxalate, cobalt oxide, cobaltous hydroxide, Xiao Suangu, rose vitriol, cobalt chloride, cobaltous dihydroxycarbonate, Cobaltous diacetate, cobalt oxalate, nickel oxide, nickel hydroxide, nickelous nitrate, single nickel salt, nickelous chloride, basic nickel carbonate, nickel acetate, nickelous oxalate and/or their combination;
Described sulfur-bearing precursor is meant S
8And/or can produce S by chemical reaction
8The sulfur-bearing precursor, contain S
2-Sulfide and/or can produce S by chemical reaction
2-Sulfur-bearing precursor, polysulfide and/or can produce the precursor of polysulfide and/or their combination by chemical reaction;
Described reductive agent is meant the organic molecule that contains oh group, comprises the carboxylic acid, polycarboxylic acid salt, polyalcohols organic molecule and/or their combination that contain a plurality of hydroxyls.
6. the preparation method of claim 5 is characterized in that, the described group vib element precursor that contains is meant sulphur ammonium molybdate, sulphur ammonium tungstate and/or their combination.
7. the preparation method of claim 5 is characterized in that, described group VIII element precursor is meant iron acetate, Cobaltous diacetate, nickel acetate and/or their combination.
8. the preparation method of claim 5 is characterized in that, described sulfur-bearing precursor is meant thiocarbamide, (NH
4)
2S, (NH
4)
2S
x, S
8And/or their combination, wherein (NH
4)
2S
xX＞1.
9. claim 5 or 8 preparation method is characterized in that described sulfur-bearing precursor is meant S
8
10. the preparation method of claim 5, it is characterized in that described reductive agent is meant: oxalic acid, citric acid, ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), ammonium oxalate, ammonium citrate, ethylenediamine tetraacetic acid (EDTA) ammonium, nitrilotriacetic acid(NTA) ammonium, ethylene glycol, glycerol, dihydroxyl propyl alcohol, dihydroxyl butanols and/or their combination.
11. the preparation method of claim 5, it is levied and is, described temperature of reaction is meant 120 ℃ to 210 ℃.
12. the preparation method of claim 5 is characterized in that, described inert atmosphere is meant not the gas that reacts with the nanometer sulfide catalyzer, comprises nitrogen, helium, neon, argon gas and/or their combination.
13. the application of the described catalyzer of claim 1 in hydrogenating desulfurization, 280 ℃-340 ℃ of temperature, liquid hourly space velocity is 0.5-30h
-1, hydrogen pressure is 2-10MPa, hydrogen to oil volume ratio is to react under the reaction conditions of 150-600.
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| JPH0576766A (en) * | 1991-09-20 | 1993-03-30 | Cosmo Oil Co Ltd | Production of catalyst for hydrodesulfurization of hydrocarbon oil |
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