CN102268284A - Hydrorefining method of medium-low distillate oil - Google Patents
Hydrorefining method of medium-low distillate oil Download PDFInfo
- Publication number
- CN102268284A CN102268284A CN2011101912839A CN201110191283A CN102268284A CN 102268284 A CN102268284 A CN 102268284A CN 2011101912839 A CN2011101912839 A CN 2011101912839A CN 201110191283 A CN201110191283 A CN 201110191283A CN 102268284 A CN102268284 A CN 102268284A
- Authority
- CN
- China
- Prior art keywords
- pseudo
- boehmite
- slurries
- molybdenum
- medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a medium-low distillate oil hydrofining method. The catalyst is a molybdenum-nickel hydrogenation catalyst, and the hydrogenation process conditions are as follows: the inlet temperature is 200-300 ℃, the operating pressure is more than or equal to 2.4MPa, and the liquid volume airspeed is 1-5 h-1The volume ratio of hydrogen to oil is 100-500; the molybdenum-nickel catalyst takes silicon-containing alumina as a carrier, molybdenum and nickel as active components, and phosphorus and alkali metal are added as auxiliaries; the precursor of the silicon-containing alumina carrier is pseudo-boehmite containing amorphous silica-alumina, which is obtained by firstly preparing amorphous silica-alumina slurry and pseudo-boehmite slurry, mixing and aging the two slurries, and then carrying out post-treatment processes including filtering, washing and drying. The method is adopted to hydrofining the first-stage hydrogenation product of the middle-low fraction pyrolysis gasoline, and the bromine number in the hydrogenation product is less than 1.0 multiplied by 10-2g/g, the sulfur content is less than 1.0 mu g/g, and the requirements of the pyrolysis gasoline on second-stage hydrogenation are met.
Description
Technical field
The present invention relates to a kind of hydrofinishing process of medium-low distillate oil, hang down the hydrofining of two sections of cut fraction pyrolysis gasoline during this method is specially adapted to.
Background technology
Pyrolysis gasoline is the byproduct in the ethylene production, its output is more than 50%～80% of ethylene production capacity, wherein aromaticity content is up to more than 50%, it is important aromatic hydrocarbon resource, wherein contain the height unsaturated hydrocarbons, as: diolefin, vinylbenzene etc. are general as the extractive raw material of aromatic hydrocarbons behind two-stage hydrogenation.In recent years, ethylene industry has obtained unprecedented development, and ethylene production capacity improves year by year, and will have significantly as the output of the pyrolysis gasoline of the important by-product of ethene increases.And be that the hydrogen addition technology of core is an important branch in the field of hydrogenation with the pyrolysis gasoline hydrogenation catalyst, in the aftertreatment of preparing ethylene by steam cracking technology, occupy very important position.
Along with the increasingly stringent of environmental legislation, more and more harsher to the requirement of sulphur content in the oil product and nitrogen content; Simultaneously since crude quality worse and worse, foreign matter contents such as sulphur, nitrogen are more and more higher, and are therefore also more and more higher to the requirement of Hydrobon catalyst.For example when coker gas oil is carried out hydrofining, the nitrogen compound of high level especially basic nitrogen compound can be adsorbed on the acidic site of catalyzer, cause the catalyst desulfurizing denitrification activity to descend, be a kind of novel carriers material of exploitation or improve the catalyst activity component concentration and improve the emphasis that Hydrobon catalyst removes the impurity ability.People are when being optimized alumina supporter specific surface area, pore volume and aperture, by introducing modifying elements such as silicon, titanium, phosphorus, come the modulation alumina supporter surface acidity, improve the strong interaction between active ingredient and alumina supporter or new synergistic effect occurs.Have the amorphous aluminum silicide specific surface area height that divergence hole distributes, anti-agglutinatting property can be good, and have certain acid catalysis activity, therefore often be used in the Hydrobon catalyst preparation process, but there is the relatively poor defective of formability in amorphous aluminosilicate.At present, the preparation method of siliceous aluminum oxide is a lot, concludes to get up to be mainly two kinds, and a kind of is to add a spot of aluminum oxide in silico-aluminate (2～10wt%) as structural promoter; Another kind is to add a spot of silico-aluminate in aluminum oxide, comes modulation alumina surface acidity, improves its specific surface area.
US4721696 discloses a kind of employing pH swing method and has prepared siliceous method of alumina, mainly be used as the carrier of sulfur-bearing and metallic impurity material hydrotreating catalyst, silicone content generally is no more than 15wt%, and silicon oxide mainly is to be purpose as structural stabilizing agent rather than so that more acid sites to be provided.
CN1267187C discloses a kind of silica-alumina that contains structure of similar to thin diaspore, described carrier silica content height, and be with silicon-containing compound solution directly or and stream be incorporated in the pseudo-boehmite slurries, purpose is that the aluminium content that increases four-coordination improves the amount of aluminum oxide strength of acid and acid, the siliceous aluminum oxide of preparation has very high cracking activity, but higher cracking activity has reduced liquid yield as catalyst carrier for hydrgenating.
CN1074303C has proposed the manufacture method of a kind of aluminum oxide and monox composite oxides, it mixes the solution in salic source and the solution in silicon oxide-containing source earlier, in mixing solutions, add hydrochloric acid then and obtain colloidal sol, in colloidal sol, add sodium hydroxide again and obtain gel, alumina source in the gel and silica source are reacted under high temperature, high pressure obtain the powdery silico-aluminate.But the composite oxides of this method preparation have a large amount of micropores, are unsuitable for the carrier as the medium-low distillate oil Hydrobon catalyst.
CN1048957C discloses and has prepared method amorphous, the catalytic activity silica-alumina, adopt tetraalkylammonium hydroxide, tri-alkoxy aluminium and positive silicic acid tetraalkyl ester hydrolysis and gel to obtain, this gel has the hole dimension that can control, and its specific surface area is at least 500m
2/ g, the mol ratio of silicon-dioxide and aluminium sesquioxide was at least 30: 1.This silica-alumina gel is mainly used in lighter hydrocarbons isomery and oligomerizing.
CN1306977C discloses a kind of silica-alumina and preparation method thereof, concrete steps are to adopt coprecipitation method to prepare a kind of salic water mixed liquid earlier, introduce a kind of solution of silicon-containing compound again, be a kind of mother liquor of synthesis of molecular sieve, make silica-alumina through aging, drying.This carrier is mainly used in the preparation of catalytic cracking catalyst.
Summary of the invention
The object of the present invention is to provide a kind of medium-low distillate oil hydrofinishing process, particularly a kind of hydrofinishing process that is used for two sections of low cut fraction pyrolysis gasoline.
Medium-low distillate oil hydrofinishing process provided by the invention, use the molybdenum nickel catalyst, it is characterized in that the hydrogenation technique condition is: 200～300 ℃ of temperature ins (preferred 220～280 ℃), working pressure 〉=2.4MPa (preferred 2.4～3.0Mpa), liquid volume air speed 1～5h
-1(preferred 2～4h
-1), hydrogen to oil volume ratio 100～500 (preferred 200～400); The molybdenum nickel catalyst is a carrier with siliceous aluminum oxide, with molybdenum, nickel is active ingredient, add phosphorus and basic metal as auxiliary agent, in catalyst weight, contain molybdenum oxide 20～30wt%, nickel oxide 2～10wt%, phosphorous oxides 0.8～5wt%, basic metal and/or alkaline earth metal oxide 1～5wt%, silicon oxide 2.5～25wt%, specific surface area of catalyst 200～300m
2/ g, pore volume 0.5～0.8ml/g; Wherein the presoma of siliceous alumina supporter is the pseudo-boehmite that contains amorphous aluminum silicide, it is by at first preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries, above-mentioned amorphous aluminum silicide slurries are mixed, wear out according to the ratio of silica content 5～40wt% with the pseudo-boehmite slurries, digestion time is 10～30min, obtains through comprising filtration, washing, exsiccant last handling process then.If the siliceous alumina supporter of other method preparation can not reach effect of the present invention even if same catalyzer is formed.
In reactor, mainly carry out hydrogenating desulfurization and olefin saturation.Reactor insulation fix bed reactor preferably among the present invention.
The present invention also provides a kind of hydrorefined catalyzer of medium-low distillate oil that is applicable to, uses this catalyzer can obtain excellent especially desulfurization and alkene saturation effect.
Support of the catalyst can add one or more in phosphorus, basic metal, the alkaline-earth metal before extruded moulding.Recommend to adopt the method for one of the following to obtain:
Method one: will contain the pseudo-boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h obtain support of the catalyst.
Method two: siliceous alumina supporter is by one or more acquisitions that add basic metal, alkaline-earth metal, phosphoric before extruded moulding.As the pseudo-boehmite that will contain amorphous aluminum silicide and precursor, nitric acid, the water mixer kneader of basic metal, alkaline-earth metal and/or phosphoric, extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h obtain support of the catalyst.
Method three: in containing the pseudo-boehmite of amorphous aluminum silicide, add after nitric acid, water mediates, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, flood the precursor solutions such as soluble salt of basic metal, alkaline-earth metal and/or phosphoric then, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h make support of the catalyst.
The preparation method that Hydrobon catalyst can adopt the present invention to recommend obtains: the aqueous solution that will contain molybdenum and nickel soluble salt impregnated on the carrier, and dry back makes catalyzer at 300～500 ℃ of following roasting 3～6h.
Basic metal and/or alkaline-earth metal and auxiliary agent phosphorus all can add when the preparation carrier, also can be after the carrier moulding, molybdenum, nickel are added in the carrier before adding in advance, the aqueous solution that will contain molybdenum, nickel soluble salt again impregnated on the siliceous alumina supporter, and dry back makes catalyzer at 300～500 ℃ of following roasting 3～6h.Can also be when dipping molybdenum, nickel, add simultaneously with molybdenum, nickel, be about to basic metal, alkaline-earth metal and/or phosphoric and be added to the aqueous solution that contains molybdenum, nickel soluble salt and impregnated on the siliceous alumina supporter, dry back makes catalyzer at 300～500 ℃ of following roasting 3～6h.
Can be more specifically in containing the pseudo-boehmite of amorphous aluminum silicide, add nitric acid, water carries out mixer kneader, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h flood the soluble salt solution of basic metal, alkaline-earth metal and/or phosphoric, 80～120 ℃ of oven dry then, 400～700 ℃ of roasting 4～6h, with the aqueous solution dipping that contains molybdenum, nickel soluble salt, dry back makes catalyzer at 300～500 ℃ of following roasting 3～6h again.
The most outstanding characteristics of the employed Hydrobon catalyst of the hydrorefined method of medium-low distillate oil of the present invention are that the presoma of the employed siliceous alumina supporter of catalytic amount is the pseudo-boehmite that contains amorphous aluminum silicide, having selected it is to mix with preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries earlier, aging, and include filtration, the exsiccant last handling process obtains, the mixing process of these amorphous aluminum silicide slurries and pseudo-boehmite slurries, both being different from simple and mechanical mixing of two kinds of powders of amorphous aluminum silicide and pseudo-boehmite, is not again the structure of amorphous aluminum silicide coated alumina type.With two bursts of mixing of materials, one side amorphous aluminum silicide and pseudo-boehmite interaction; On the other hand, also be accompanied by reaction between a spot of free aluminum ion and the silicate ion.
The present invention also provides a kind of preparation method who contains the pseudo-boehmite of amorphous aluminum silicide, it is characterized in that amorphous aluminum silicide slurries and pseudo-boehmite slurries and stream mix or a kind of material joined in the another kind of material mixing, after mixing finishes, aging 10～30min, filter, wash to sodium ions content less than 0.5wt%, at 80～120 ℃ of down dry 2～20h, obtain containing the pseudo-boehmite of amorphous aluminum silicide.Its specific surface area is preferably 250～400m
2/ g, pore volume is preferably 0.7～1.4ml/g, and infrared acidity is preferably 0.28～0.55mmol/g, so that the catalyzer that makes at last satisfies requirement of the present invention.
The preparation process of pseudoboehmite that contains amorphous aluminum silicide provided by the invention comprises the preparation of amorphous aluminum silicide slurries and the preparation of pseudo-boehmite slurries, and with these two kinds of slurries mixing, the mixing of two kinds of slurries can be adopted and flow to mix or a kind of slurries are joined in the another kind of slurries and mix, aging then, more after filtration, last handling processes such as washing, drying obtain containing the pseudo-boehmite of amorphous aluminum silicide.PH value of solution is preferably 9.0～10.5 when aging, and temperature is preferably 20～65 ℃, and the time is preferably 10～25min.Drying temperature is preferably 80～120 ℃.
The present invention is not particularly limited the preparation method of amorphous aluminum silicide slurries and pseudo-boehmite slurries, adopts current techique to get final product, and can adopt existing nitrate method or carborization as the preparation of pseudo-boehmite slurries.
The present invention provides a kind of preparation method of amorphous aluminum silicide slurries simultaneously, comprising:
(a) compound concentration is 10～150gAl
2O
3The sodium metaaluminate of/L or sodium aluminate solution are added in the glue jar, are controlled to 15～50 ℃ of glue jar temperature.
(b) compound concentration is 50～200gSiO
2The silicon-containing compound solution of/L joins silicon-containing compound solution in the solution of (a), control pH value 11.5～13.
(c) under the condition of low whipping speed greater than 250r/min, feed the carbon dioxide of concentration greater than 20v% continuously, the flow of control carbon dioxide is at 1～10Nm
3/ h, with time 20～40min, control endpoint pH 7.5～9.5 neutralizes and finishes in the control.
(d) in pH value 7.5～9.5, the solution 5～20min of aging (c) preparation obtains the amorphous aluminum silicide slurries under the condition that temperature is 25～40 ℃.
Preferably with carbon dioxide process preparation, silicon-containing compound can be water glass, silicon sol to amorphous aluminum silicide slurries of the present invention, water glass preferably, and concentration of sodium silicate is counted 50～200gSiO with silicon oxide
2/ L is preferably 80～120gSiO
2/ L; The concentration of sodium metaaluminate or sodium aluminate solution is counted 10～150gAl with aluminum oxide
2O
3/ L is preferably 35～110gAl
2O
3/ L; Digestion time preferably is controlled at 5～15min; Control silica alumina ratio 40～60wt% in the final amorphous aluminum silicide.
The present invention also provides a kind of preparation method of pseudo-boehmite slurries.Sodium metaaluminate or sodium aluminate solution are added in the glue jar, feed carbon dioxide through becoming glue, the aging pseudo-boehmite slurries that obtain with intermittence or successive mode.The concentration of sodium metaaluminate or sodium aluminate solution is 20～150gAl
2O
3/ L; Concentration of carbon dioxide is preferably between 40～100v% greater than 20v%, and the flow of carbon dioxide is 1～10Nm
3/ h; Become 20～65 ℃ of glue temperature, best 30～45 ℃; Become glue endpoint pH 9.0～10.5; Become glue and digestion time preferably to be no more than 40min altogether, be advisable with 25～35min.
In the preparation process of pseudo-boehmite slurries of the present invention, become glue terminal point pH preferably to be controlled at 9.0～10.5, the pH value is lower than at 9.0 o'clock, easy and the reaction of sodium bicarbonate generation silk sodium stone structure of the pseudo-boehmite that forms, the silk sodium stone that generates is a kind of insoluble salt, hindered the washing of sodium ion, might influence the use properties of aluminum oxide as carrier.
The pseudo-boehmite best surfaces acidic site that contains amorphous aluminum silicide of the present invention's preparation is based on the weak acid position.
The pseudo-boehmite that contains amorphous aluminum silicide that the present invention selects for use promptly has the high acidity of amorphous aluminum silicide, the characteristic of high-specific surface area, contains the advantage of pseudo-boehmite simultaneously, has overcome the problem of amorphous aluminum silicide moulding difference.The aluminum oxide that contains amorphous aluminum silicide of preparation is specially adapted to do the carrier of hydrogenation catalyst.
Hydrobon catalyst provided by the invention contains basic metal and/or alkaline-earth metal, can change the acid-basicity on support of the catalyst surface, helps reducing carbonaceous in the hydrogenation process, gelationus deposition, thereby prolongs the work-ing life of catalyzer.The alumina supporter physico-chemical property can be effectively regulated in the adding of auxiliary agent phosphorus, makes pore distribution concentration; Improve the weak acid of carrier, reduce strong acid; Improve the thermostability of carrier.
Method of the present invention is applicable to that the hydrogenation of alkene in the medium-low distillate oil product is saturated, and compared with prior art, this method of hydrotreating has reactive system hydrogenation activity height, and stability and anti-coking performance are strong, but advantages such as operational condition wide ranges.When using medium-low distillate oil hydrofinishing process of the present invention, adopt specific Hydrobon catalyst, hydrogenation activity and desulfurization performance height, chemical stability and Heat stability is good, the strong and long service life of anti-coking performance.
Embodiment
Preparation catalyzer agents useful for same source:
Ammonium molybdate: Shanghai gelatinizing factory
Nickelous nitrate: Xi'an chemical reagent factory
Analytical procedure:
Oil distillation: adopt petroleum products test method SYB-2110-60 to measure;
Bromine valency: adopt the ICl method to measure, show with gram bromine/100 gram oil meters;
Diene: adopt apple acid anhydrides method to measure, show with gram iodine/100 gram oil meters;
Arsenic: adopt the DV-4300 Atomic Emission SpectrometerAES to measure;
Sulphur: adopt the WK-2B Microcoulomb instrument to measure;
Colloid: adopt petroleum products test method SYB-2103-60 to measure;
Catalyst crystalline phases: adopt BRUKER D
8ADVERCE type X-ray diffractometer is measured;
Infrared acidity: adopt pyridine-infrared mensuration;
Specific surface area, pore volume: adopt low temperature N
2The method of adsorption-desorption is measured.
The embodiment preparation of catalyzer 1～7:
The preparation of catalyzer 1:
Configuration 2L concentration is 120gAl
2O
3The sodium aluminate solution of/L places in the glue jar, is controlled to 45 ℃ of glue jar temperature, under agitation condition, feeds 65v%CO
2+ 35v% Air mixing gas, the flow of carbonic acid gas is 3Nm in the gas mixture
3/ h.Stop to feed mixed gas when the pH value reaches 10.0, aging then 20min obtains the pseudo-boehmite slurries.
Configuration 2L concentration is 120gAl
2O
3The sodium aluminate solution of/L places in the glue jar, adds 2L 80gSiO then
2The sodium silicate solution of/L is controlled to 30 ℃ of glue jar temperature, feeds 60v%CO
2+ 40v% Air mixing gas, CO in the gas mixture
2Flow be 3Nm
3/ h, the control endpoint pH is 10.0, aging 15min obtains the amorphous aluminum silicide slurries.
Under continuous stirring condition, 2L amorphous aluminum silicide slurries are joined in the 1L pseudo-boehmite slurries, 45 ℃ of control mixing temperatures, aging 15min, filtration washing is to Na
+Content obtains containing the pseudo-boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 10h.
To contain the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 480 ℃ of roasting 4h use the saturated impregnated carrier of Lithium Citrate de solution then, 120 ℃ of oven dry, 600 ℃ of roasting 4h obtain the alumina supporter of siliceous, phosphorus and lithium.Nickel acetate, ammonium molybdate be dissolved in the water jointly make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 3h obtain containing the catalyzer 1 of molybdenum oxide 23.5wt%, nickel oxide 6.5wt%, Vanadium Pentoxide in FLAKES 1.5wt%, silicon oxide 16.5wt%, Lithium Oxide 98min 2.5wt%.
The preparation of catalyzer 2:
The preparation of amorphous aluminum silicide slurries is with catalyzer 1.Configuration 2L concentration is 95gAl
2O
3The sodium aluminate solution of/L places in the glue jar, is controlled to 45 ℃ of glue jar temperature, under agitation condition, feeds 65v%CO
2+ 35v% Air mixing gas, the flow of carbonic acid gas is 3Nm in the gas mixture
3/ h.Stop to feed mixed gas when the pH value reaches 10.0, aging then 20min obtains the pseudo-boehmite slurries.
Under continuous stirring condition, 3L amorphous aluminum silicide slurries are joined in the 1L pseudo-boehmite slurries, 40 ℃ of control mixing temperatures, aging 20min, filtration washing is to Na
+Content obtains containing the pseudo-boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 12h.
To contain the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 580 ℃ of roasting 4h obtain alumina supporter siliceous, phosphorus.Nickel acetate, ammonium molybdate, saltpetre is dissolved in the water jointly makes steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 400 ℃ of roasting 5h obtain containing the catalyzer 2 of molybdenum oxide 20wt%, nickel oxide 6.0wt%, silicon oxide 21.4wt%, Vanadium Pentoxide in FLAKES 2.5wt%, potassium oxide 1.0wt%.
The preparation of catalyzer 3:
Configuration 2L concentration is 100gAl
2O
3The sodium aluminate solution of/L places the one-tenth glue jar of a 8L, and the temperature that is controlled to the glue jar is 35 ℃, and under continuous stirring condition, feeding concentration is 60v%CO
2+ 40v% Air mixing gas, the flow of carbonic acid gas is 2Nm in the gas mixture
3/ h stops to feed carbonic acid gas when the pH value reaches 10.5, aging 25min obtains the pseudo-boehmite slurries.
Configuration 2L concentration is 130gAl
2O
3The sodium aluminate solution of/L places in the glue jar, adds 2L 80gSiO then
2The sodium silicate solution of/L, control reaction temperature are 25 ℃, feed 50v%CO
2+ 50v% Air mixing gas, CO
2Flow be 5Nm
3/ h, the pH value of control terminal point is 10.0, aging 10min obtains the amorphous aluminum silicide slurries.
Under continuous stirring condition, 1L pseudo-boehmite slurries are joined in the glue jar with 3L amorphous aluminum silicide slurries and stream, the control mixing temperature is at 45 ℃, and aging 15min, filtration washing are to Na
+Ion content is less than till 0.5%, and 120 ℃ of dry 12h obtain containing the pseudo-boehmite of amorphous aluminum silicide.
To contain the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 4h use the saturated impregnated carrier of saltpetre and strontium nitrate solution then, 120 ℃ of oven dry, 650 ℃ of roasting 4h obtain the alumina supporter of siliceous, phosphorus, potassium and strontium.Nickelous nitrate, ammonium molybdate be dissolved in the water jointly make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 3h obtain containing the catalyzer 3 of molybdenum oxide 28wt%, nickel oxide 3.5wt%, Vanadium Pentoxide in FLAKES 1.5wt%, silicon oxide 18.8wt%, potassium oxide 0.5wt%, strontium oxide 1.5wt%.
The preparation of catalyzer 4:
The preparation method of pseudo-boehmite slurries is with catalyzer 3.Configuration 2L concentration is 132gAl
2O
3The sodium aluminate solution of/L places in the glue jar, adds 2L 80gSiO then
2The sodium silicate solution of/L, control reaction temperature are 25 ℃, feed 50v%CO
2+ 50v% Air mixing gas, CO
2Flow be 5Nm
3/ h, the pH value of control terminal point is 9.5, aging 20min obtains the amorphous aluminum silicide slurries.
Under continuous stirring condition, 1.5L pseudo-boehmite slurries are joined in the glue jar with 1.6L amorphous aluminum silicide slurries and stream, 50 ℃ of control mixing temperatures, aging 10min, filtration washing is to Na
+Content obtains containing the pseudo-boehmite of amorphous aluminum silicide less than 0.5%, 110 ℃ of dry 15h.
To contain the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 3h use the saturated impregnated carrier of magnesium nitrate solution then, 120 ℃ of oven dry, 700 ℃ of roasting 4h obtain the alumina supporter of siliceous, phosphorus and magnesium.Nickelous nitrate, ammonium molybdate be dissolved in the water jointly make steeping fluid, be impregnated on the 100g carrier 120 ℃ of oven dry, 420 ℃ of roasting 4h, obtain containing molybdenum oxide 26wt%, nickel oxide 6wt%, silicon oxide 12.4wt%, Vanadium Pentoxide in FLAKES 2.5wt%, the catalyzer 4 of magnesium oxide 3.5wt%.
The preparation of catalyzer 5:
Configuration 2L concentration is 85gAl
2O
3The sodium aluminate solution of/L places in the glue jar, and being controlled to glue jar temperature is 50 ℃, and under continuous stirring condition, feeding concentration is 80v%CO
2+ 20v% Air mixing gas, the flow of carbonic acid gas is 4Nm in the gas mixture
3/ h stops to feed mixed gas when the pH value reaches 10.0, aging 20min obtains the pseudo-boehmite slurries.
Configuration 3L concentration is 100gAl
2O
3The sodium aluminate solution of/L places in the glue jar, adds 2L 60gSiO then
2The sodium silicate solution of/L, 30 ℃ of control reaction temperature feed 60v%CO
2+ 40v% Air mixing gas, CO in the gas mixture
2Flow be 5Nm
3/ h, the control endpoint pH is 9.5, aging 20min obtains the amorphous aluminum silicide slurries.
Under continuous stirring condition, 2L pseudo-boehmite slurries are joined in the glue jar with 1L amorphous aluminum silicide slurries and stream, 50 ℃ of control mixing temperatures, aging 15min, filtration washing is to Na
+Content obtains containing the pseudo-boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 10h.
To contain the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, Lithium Acetate, nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 550 ℃ of roasting 4h obtain the alumina supporter of siliceous, phosphorus and lithium.Nickel acetate, ammonium molybdate be dissolved in the water jointly make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 460 ℃ of roasting 4h obtain containing the catalyzer 5 of molybdenum oxide 25wt%, nickel oxide 7.0wt%, silicon oxide 5.8wt%, Vanadium Pentoxide in FLAKES 4.0wt%, Lithium Oxide 98min 2.0wt%.
The preparation of catalyzer 6:
The preparation of pseudo-boehmite slurries and amorphous aluminum silicide slurries is with catalyzer 3.
Under continuous stirring condition, 2L pseudo-boehmite slurries are joined in the glue jar with 2L amorphous aluminum silicide slurries and stream, the control mixing temperature is at 45 ℃, and aging 15min, filtration washing are to Na
+Ion content is less than till 0.5%, and 120 ℃ of dry 12h obtain containing the pseudo-boehmite of amorphous aluminum silicide.
To contain the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 4h use the saturated impregnated carrier of potassium nitrate solution then, 120 ℃ of oven dry, 600 ℃ of roasting 4h obtain the alumina supporter of siliceous, phosphorus and potassium.Nickelous nitrate, ammonium molybdate be dissolved in the water jointly make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 3h obtain containing the catalyzer 6 of molybdenum oxide 26wt%, nickel oxide 4.0wt%, Vanadium Pentoxide in FLAKES 2.5wt%, silicon oxide 12.8wt%, potassium oxide 2.0wt%.
The preparation of catalyzer 7:
The preparation of pseudo-boehmite slurries and amorphous aluminum silicide slurries is with catalyzer 5.
Under continuous stirring condition, 2L pseudo-boehmite slurries are joined in the glue jar with 2L amorphous aluminum silicide slurries and stream, 55 ℃ of control mixing temperatures, aging 10min, filtration washing is to Na
+Content obtains containing the pseudo-boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 10h.
To contain the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, magnesium acetate, nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 550 ℃ of roasting 4h obtain the alumina supporter of siliceous, phosphorus and magnesium.Nickel acetate, ammonium molybdate be dissolved in the water jointly make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 450 ℃ of roasting 4h obtain containing the catalyzer 7 of molybdenum oxide 24wt%, nickel oxide 6.0wt%, silicon oxide 9.2wt%, Vanadium Pentoxide in FLAKES 4.0wt%, magnesium oxide 1.0wt%.
Embodiment is as shown in table 1 with the physico-chemical property of catalyzer 1～7.
Testing raw materials used is Lanzhou Petrochemical Company cracking C
6～C
8Middle runnings and C
5～C
9The full-fraction one-stage hydrogenated products, its character sees Table 2.
The table 1 embodiment physico-chemical property of catalyzer 1～7
Table 2 hydrogenating materials oil nature
Embodiment 1
Live catalyst 1 is packed in the 100ml adiabatic reactor reaction unit, carry out the sulfuration of catalyzer earlier: dithiocarbonic anhydride is joined the vulcanized oil that is made in the hexanaphthene about sulphur content 1000 μ g/g, reactor is warmed up to 240 ℃ and begins into vulcanized oil, pressure 2.5Mpa, vulcanized oil volume space velocity 3.0h
-1, hydrogen/vulcanized oil volume ratio 300: 1, the temperature rise rate with 10 ℃/h is warmed up to 350 ℃ then, keeps 25h, finishes the sulfidizing to catalyzer.
Sulfidizing is a raw material with stock oil 1, in 220 ℃ of temperature ins, reaction pressure 2.4MPa, liquid volume air speed: 4h after finishing
-1, hydrogen and oil volume are than the 200h that turns round under 300 conditions.Bromine valency and sulphur content in every 24h sampling analysis product the results are shown in Table 3.
Embodiment 2
Live catalyst 2 is packed in the 100ml adiabatic reactor reaction unit, and the catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing is a raw material with stock oil 2, in 240 ℃ of temperature ins, reaction pressure 2.6MPa, liquid volume air speed: 4.5h after finishing
-1, hydrogen and oil volume are than the 200h that turns round under 350 conditions.Bromine valency and sulphur content in every 24h sampling analysis product the results are shown in Table 3.
Embodiment 3
Live catalyst 3 is packed in the 100ml adiabatic reactor reaction unit, and the catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing is a raw material with stock oil 3, in 280 ℃ of temperature ins, reaction pressure 3.0MPa, liquid volume air speed: 2h after finishing
-1, hydrogen and oil volume are than the 200h that turns round under 450 conditions.Bromine valency and sulphur content in every 24h sampling analysis product the results are shown in Table 3.
Embodiment 4
Live catalyst 4 is packed in the 100ml adiabatic reactor reaction unit, and the catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing is a raw material with stock oil 4, in 250 ℃ of temperature ins, reaction pressure 2.6MPa, liquid volume air speed: 3.5h after finishing
-1, hydrogen and oil volume are than the 200h that turns round under 400 conditions.Bromine valency and sulphur content in every 24h sampling analysis product the results are shown in Table 3.
Embodiment 5
Live catalyst 5 is packed in the 100ml adiabatic reactor reaction unit, and the catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing is a raw material with stock oil 4, in 250 ℃ of temperature ins, reaction pressure 2.8MPa, liquid volume air speed: 3.5h after finishing
-1, hydrogen and oil volume are than the 200h that turns round under 300 conditions.Bromine valency and sulphur content in every 24h sampling analysis product the results are shown in Table 3.
Embodiment 6
Live catalyst 6 is packed in the 100ml adiabatic reactor reaction unit, and the catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing is a raw material with stock oil 2, in 260 ℃ of temperature ins, reaction pressure 2.6MPa, liquid volume air speed: 4.0h after finishing
-1, hydrogen and oil volume are than the 200h that turns round under 300 conditions.Bromine valency and sulphur content in every 24h sampling analysis product the results are shown in Table 3.
Embodiment 7
Live catalyst 7 is packed in the 100ml adiabatic reactor reaction unit, and the catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing is a raw material with stock oil 4 after finishing, at temperature in 250C, and reaction pressure 2.8MPa, liquid volume air speed: 3.0h
-1, hydrogen and oil volume are than the 200h that turns round under 400 conditions.Bromine valency and sulphur content in every 24h sampling analysis product the results are shown in Table 3.
Comparative Examples 1
This Comparative Examples uses the presoma of support of the catalyst to be the silica-alumina powder, according to the 3 described method preparations of embodiment among the CN1267187C; Preparation of catalysts method and composition are with embodiment catalyzer 3.
The catalyst vulcanization treatment process is with embodiment 1; The evaluating catalyst condition the results are shown in Table 3 with embodiment 3.
Comparative Examples 2
This Comparative Examples uses the presoma of support of the catalyst according to the 1 described method preparation of embodiment among the CN1074303C; Preparation of catalysts method and composition are with embodiment catalyzer 4.
The catalyst vulcanization treatment process is with embodiment 1; The evaluating catalyst condition the results are shown in Table 3 with embodiment 4.
Comparative Examples 3
This Comparative Examples uses the presoma of support of the catalyst according to the 4 described method preparations of embodiment among the CN1306977C; Preparation of catalysts method and composition are with embodiment catalyzer 2.
The catalyst vulcanization treatment process is with embodiment 1; The evaluating catalyst condition the results are shown in Table 3 with embodiment 2.
Comparative Examples 4
This Comparative Examples uses the presoma of support of the catalyst to be industrial amorphous aluminum silicide (SiO
2Content 45%); The Preparation of catalysts method is with embodiment catalyzer 2.Catalyzer consists of: molybdenum oxide 20wt%, nickel oxide 6wt%, silicon oxide 31.7wt%, Vanadium Pentoxide in FLAKES 2.5wt%, potassium oxide 1.0wt%.
The catalyst vulcanization treatment process is with embodiment 1; The evaluating catalyst condition the results are shown in Table 3 with embodiment 2.
Comparative Examples 5
This Comparative Examples uses the presoma of support of the catalyst to be industrial pseudo-boehmite; The Preparation of catalysts method with embodiment with catalyzer 1, this catalyzer oxygen-free silicon, all the other are formed with catalyzer 1.
Catalyst vulcanization treatment process and evaluating catalyst condition are with embodiment 1, and bromine valency and sulphur content in every 24h sampling analysis product the results are shown in Table 3.
As shown in Table 3, the present invention's low cut fraction pyrolysis gasoline one-stage hydrogenation product of hydrogenation catalyst centering of containing the pseudo-boehmite preparation of amorphous aluminum silicide by employing carries out hydrofining, bromine valency＜1.0 * 10 in the hydrogenated products
-2G/g, sulphur content＜1.0 μ g/g meets the requirement of pyrolysis gasoline secondary hydrogenation.
Table 3 embodiment 1～7 and Comparative Examples 1～5 hydrogenation result
Claims (15)
1. medium-low distillate oil hydrofinishing process, catalyst system therefor is the molybdenum nickel series hydrogenating catalyst, it is characterized in that the hydrogenation technique condition is: 200～300 ℃ of temperature ins, working pressure 〉=2.4MPa, liquid volume air speed 1～5h
-1, hydrogen to oil volume ratio 100～500; The molybdenum nickel catalyst is a carrier with siliceous aluminum oxide, with molybdenum, nickel is active ingredient, add phosphorus and basic metal as auxiliary agent, in catalyst weight, contain molybdenum oxide 20～30wt%, nickel oxide 2～10wt%, phosphorous oxides 0.8～5wt%, basic metal and/or alkaline earth metal oxide 1～5wt%, silicon oxide 2.5～25wt%, specific surface area of catalyst 200～300m
2/ g, pore volume 0.5～0.8ml/g; Wherein the presoma of siliceous alumina supporter is the pseudo-boehmite that contains amorphous aluminum silicide, it is by at first preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries, above-mentioned amorphous aluminum silicide slurries are mixed, wear out according to the ratio of silica content 5～40wt% with the pseudo-boehmite slurries, digestion time is 10～30min, obtains through comprising filtration, washing, exsiccant last handling process then.
2. medium-low distillate oil hydrofinishing process according to claim 1 is characterized in that in the hydrogenation technique condition that temperature in is 220～280 ℃.
3. medium-low distillate oil hydrofinishing process according to claim 1 is characterized in that in the hydrogenation technique condition that working pressure is 2.4～3.0MPa.
4. medium-low distillate oil hydrofinishing process according to claim 1 is characterized in that in the hydrogenation technique condition that the liquid volume air speed is 2～4h
-1
5. medium-low distillate oil hydrofinishing process according to claim 1 is characterized in that in the hydrogenation technique condition that hydrogen to oil volume ratio is 200～400.
6. medium-low distillate oil hydrofinishing process according to claim 1, the pseudo-boehmite that it is characterized in that containing amorphous aluminum silicide is by with amorphous aluminum silicide slurries and pseudo-boehmite slurries and stream mixes or a kind of slurries are joined in the another kind of slurries mix, after mixing was finished, pH value of solution was 9.0～10.5 when aging.
7. according to claim 1 or 6 described medium-low distillate oil hydrofinishing process, temperature is 20～65 ℃ when it is characterized in that wearing out.
8. according to claim 1 or 6 described medium-low distillate oil hydrofinishing process, it is characterized in that the amorphous aluminum silicide slurries obtain by following method:
(a) compound concentration is 10～150gAl
2O
3The sodium metaaluminate of/L or sodium aluminate solution join in the glue jar, are controlled to 15～50 ℃ of glue jar temperature;
(b) compound concentration is 50～200gSiO
2The silicon-containing compound solution of/L joins in the sodium aluminate solution of (a), control pH value 11.5～13;
(c) under the condition of low whipping speed greater than 250r/min, feed the carbon dioxide of concentration greater than 20v% continuously, the flow of control carbon dioxide is at 1～10Nm
3/ h, in and time 20～40min, endpoint pH 7.5～9.5, neutralization finishes;
(d) in pH value 7.5～9.5, aging (c) 5～20min obtains the amorphous aluminum silicide slurries under the condition that temperature is 25～40 ℃.
9. according to claim 1 or 6 described medium-low distillate oil hydrofinishing process, it is characterized in that the pseudo-boehmite slurries obtain by following method: sodium metaaluminate or sodium aluminate solution are placed in the glue jar, feed carbon dioxide with intermittence or continuous mode and become glue, the aging pseudo-boehmite slurries that obtain; The concentration of sodium metaaluminate or sodium aluminate solution is 20～150gAl
2O
3/ L; Gas concentration lwevel is greater than 20v%, flow 1～10Nm
3/ h; Become 20～65 ℃ of glue temperature; Become glue endpoint pH 9.0～10.5, become in the glue and time and digestion time sum less than 40min.
10. medium-low distillate oil hydrofinishing process according to claim 1 is characterized in that the molybdenum nickel catalyst is to impregnated on the siliceous alumina supporter by the aqueous solution that will contain molybdenum, nickel soluble salt, and dry back makes at 300～500 ℃ of following roasting 3～6h.
11. medium-low distillate oil hydrofinishing process according to claim 10, it is characterized in that siliceous alumina supporter is pseudo-boehmite by will containing amorphous aluminum silicide and nitric acid, water mixer kneader, extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h make.
12. medium-low distillate oil hydrofinishing process according to claim 10, it is characterized in that siliceous alumina supporter is pseudo-boehmite by will containing amorphous aluminum silicide and nitric acid, water mixer kneader, in adding basic metal, alkaline-earth metal, the boron one or more, extruded moulding then, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h make
13. medium-low distillate oil hydrofinishing process according to claim 10, it is characterized in that the molybdenum nickel catalyst is by basic metal, alkaline-earth metal and/or boron are added in the siliceous alumina supporter before adding at molybdenum, nickel in advance, impregnated in the aqueous solution that contains molybdenum, nickel soluble salt again, dry back makes at 300～500 ℃ of following roasting 3～6h.
14. medium-low distillate oil hydrofinishing process according to claim 10, it is characterized in that the molybdenum nickel catalyst is to impregnated on the siliceous alumina supporter by basic metal, alkaline-earth metal and/or boron being added to the aqueous solution that contains molybdenum, nickel soluble salt, dry back makes at 300～500 ℃ of following roasting 3～6h.
15. medium-low distillate oil hydrofinishing process according to claim 13, it is characterized in that the molybdenum nickel catalyst be by in containing the pseudo-boehmite of amorphous aluminum silicide, add nitric acid, water carries out mixer kneader, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, flood the soluble salt solution of basic metal, alkaline-earth metal and/or boron then, 80～120 ℃ of oven dry, 400～700 ℃ of roasting 4～6h, impregnated in the aqueous solution that contains molybdenum, nickel soluble salt again, dry back makes at 300～500 ℃ of following roasting 3～6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110191283.9A CN102268284B (en) | 2011-07-08 | 2011-07-08 | Hydrorefining method of medium-low distillate oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110191283.9A CN102268284B (en) | 2011-07-08 | 2011-07-08 | Hydrorefining method of medium-low distillate oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102268284A true CN102268284A (en) | 2011-12-07 |
| CN102268284B CN102268284B (en) | 2014-04-02 |
Family
ID=45050750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110191283.9A Active CN102268284B (en) | 2011-07-08 | 2011-07-08 | Hydrorefining method of medium-low distillate oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102268284B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107511128A (en) * | 2016-06-16 | 2017-12-26 | 中国石油天然气股份有限公司 | Pretreatment method of adsorption desulfurizer |
| CN108264586A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Hydrogenation method of C-V petroleum resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218089A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Catalyst carrier containing difunctional amorphous aluminum silicide and preparation thereof |
| CN1250746A (en) * | 1998-10-13 | 2000-04-19 | 中国石油化工集团公司 | Process for preparing artificial diasporite and gamma-alumina |
| CN1597093A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Method of preparing amorphous silica-alumina using carbonization |
| CN101037614A (en) * | 2006-03-17 | 2007-09-19 | 中国石油天然气股份有限公司 | Hydrofining catalyst, preparation method and application |
-
2011
- 2011-07-08 CN CN201110191283.9A patent/CN102268284B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218089A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Catalyst carrier containing difunctional amorphous aluminum silicide and preparation thereof |
| CN1250746A (en) * | 1998-10-13 | 2000-04-19 | 中国石油化工集团公司 | Process for preparing artificial diasporite and gamma-alumina |
| CN1597093A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Method of preparing amorphous silica-alumina using carbonization |
| CN101037614A (en) * | 2006-03-17 | 2007-09-19 | 中国石油天然气股份有限公司 | Hydrofining catalyst, preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107511128A (en) * | 2016-06-16 | 2017-12-26 | 中国石油天然气股份有限公司 | Pretreatment method of adsorption desulfurizer |
| CN107511128B (en) * | 2016-06-16 | 2020-01-03 | 中国石油天然气股份有限公司 | Pretreatment method of adsorption desulfurizer |
| CN108264586A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Hydrogenation method of C-V petroleum resin |
| CN108264586B (en) * | 2016-12-30 | 2020-07-14 | 中国石油天然气股份有限公司 | Hydrogenation method of C-V petroleum resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102268284B (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102268283B (en) | Hydrorefining method of distillate oil | |
| CN102335612B (en) | Selective hydrodesulfurization catalyst and preparation method thereof | |
| CN102139217B (en) | Selective hydrogenation catalyst and preparation method thereof | |
| CN102319579B (en) | Hydrofining catalyst and preparation method thereof | |
| RU2569682C2 (en) | Composition and method for preparation of carrier and catalyst of deep hydrofining of hydrocarbon stock | |
| CN102319577B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN102451694B (en) | Hydro-sweetening Catalysts and its preparation method and application | |
| CN102139204A (en) | Pseudo-boehmite containing amorphous silica-alumina and preparation method thereof | |
| CN102994144B (en) | Petroleum hydrocarbon cracking carbon four and carbon five fraction saturated hydrogenation method | |
| CN106622204A (en) | Zinc oxide material containing zinc-aluminum spinel and preparation method thereof | |
| CN102319578A (en) | Hydrofining catalyst and preparation method thereof | |
| CN101259420B (en) | Hydrogenation catalysts and its manufacturing method and use | |
| CN102989477A (en) | Nickel-based hydrogenation catalyst, preparation method thereof and reduction and regeneration method of catalyst | |
| CN102352265B (en) | Method for producing catalytic reforming raw material | |
| CN106179414A (en) | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof | |
| CN102268285B (en) | Pre-hydrogenation treatment method for reforming raw material | |
| CN102039154B (en) | Hydrogenation sweetening catalyst, preparing method and application thereof | |
| CN102268284B (en) | Hydrorefining method of medium-low distillate oil | |
| CN113083356B (en) | Mesomicroporous ZSM-5/alumina catalyst and its preparation and application | |
| CN102994145B (en) | Petroleum hydrocarbon cracking carbon nine fraction saturated hydrogenation method | |
| CN102295955B (en) | Hydro-upgrading method for inferior gasoline | |
| CN102319572B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN102994143A (en) | Petroleum hydrocarbon cracking carbon four and carbon five fraction saturated hydrogenation method | |
| CN106929091B (en) | Catalytic gasoline hydrodesulfurization modification method | |
| CN102039134B (en) | Light oil hydrogenation sweetening catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |