CN102268285B - Pre-hydrotreatment method of reforming feedstocks - Google Patents
Pre-hydrotreatment method of reforming feedstocks Download PDFInfo
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Abstract
The invention provides a pre-hydrotreatment method of reforming feedstocks. The pre-hydrotreatment process undergoes in the conditions that: the reaction inlet is at a temperature of 200-320DEG C, the operation pressure is over 2.4MPa, the volume space velocity of fresh raw oil is 4-12h<-1>, and the volume ratio of hydrogen to oil is 50-300; the hydrotreatment catalyst employed takes silicon-containing alumina as the carrier, cobalt and molybdenum as the active constituents, boron and alkali metal and/or alkaline earth metal as the auxiliary agents, and the precursor of the silicon-containing alumina carrier is amorphous silica-alumina containing pseudo-boehmite, which is obtained by preparation of an amorphous silica-alumina slurry and a pseudo-boehmite slurry first, followed by mixing and ageing of the two slurries, and the post-treatments of filtering, washing and drying. The method of the invention can be used to treat catalytic reforming feedstocks of high sulfur and nitrogen content as well as high olefin content in a low pressure condition, and can provide qualified feedstocks with sulfur and nitrogen content both less than 0.5 microgram/gram for catalytic reforming units.
Description
Technical field
The present invention relates to a kind of pre-hydrotreatment method of reforming feedstocks, be specially adapted to the hydrogen pretreatment that adds of catalytic reforming unit charging.
Background technology
Catalytic reforming process is one of important technique of oil refining and petrochemical complex, and it is with C
6～C
11Naphtha fraction is raw material, reacts and produces the reformation be rich in aromatic hydrocarbons and produce oil by catalytic hydroprocessing, simultaneously by-product hydrogen.Catalytic reforming process adopts two (many) noble metal catalysts such as platinum-rhenium and platinum-iridium usually, for preventing poisoning of catalyst, requires sulphur, nitrogen content in its charging all to be less than 0.5 μ g/g.Therefore, need raw material first to carry out pre-hydrotreating before advancing reformer, to remove in stock oil the impurity harmful to catalytic reforming catalyst, comprising sulphur, nitrogen, alkene and arsenic, lead, copper and moisture etc.
In recent years, along with the increasingly stringent of environmental legislation, more and more harsher to the requirement of Sulfur Content in Petroleum Products and nitrogen content; Simultaneously due to crude quality worse and worse, the foreign matter contents such as sulphur, nitrogen are more and more higher, therefore also more and more higher to the requirement of hydrotreating catalyst.For example, when coker gas oil is carried out to hydrotreatment, 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, and the emphasis of raising hydrotreating catalyst imurity-removal ability is a kind of novel carriers material of exploitation or improve the catalyst activity component concentration.People are when being optimized alumina supporter specific surface area, pore volume and aperture, by introducing the 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.Amorphous aluminum silicide specific surface area with divergence hole distribution is high, and anti-sintering property is good, and has certain surface acidity, therefore in the hydrotreating catalyst preparation process, often be used, but there is the poor defect of formability in amorphous aluminosilicate.At present, the preparation method of silicon-containing alumina is a lot, is summed up and is mainly two kinds, and a kind of is in silico-aluminate, to add a small amount of aluminum oxide (2～10wt%) as structural promoter; Another kind is to add a small amount of silico-aluminate in aluminum oxide, carrys out modulation alumina surface acidity, improves its specific surface area.
US4721696 discloses a kind of method that the pH of employing swing method prepares silicon-containing 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 is mainly as structural stabilizing agent rather than take the acid sites that provides more is purpose.
CN1267187C discloses a kind of silica-alumina containing structure of similar to thin diaspore, described carrier silica content is high, and be by 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 aluminum oxide strength of acid and sour amount, the silicon-containing alumina of preparation has very high cracking activity, but higher cracking activity, as catalyst carrier for hydrgenating, has reduced liquid yield.
CN1074303C has proposed the manufacture method of a kind of aluminum oxide and monox composite oxides, it first mixes the solution in the solution in salic source and silicon oxide-containing source, then in mixing solutions, add hydrochloric acid to obtain colloidal sol, in colloidal sol, add sodium hydroxide to obtain gel again, finally make alumina source and silica source in gel react and obtain the powdery silico-aluminate under high temperature, high pressure.But composite oxides prepared by the method have a large amount of micropores, be unsuitable for the carrier as the medium-low distillate oil hydrotreating 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 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 is 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 first to prepare a kind of salic water mixed liquid, introduce again a kind of solution of silicon-containing compound, be a kind of mother liquor of synthesis of molecular sieve, through aging, drying, make silica-alumina.This carrier is mainly used in the preparation of catalytic cracking catalyst.
CN100448951C discloses a kind of method of producing catalytic reforming raw material, mainly middle matter gasoline fraction and virgin naphtha after the cutting of secondary processing of gasoline raw material are carried out to twice hydrofining, the first Hydrobon catalyst: take aluminum oxide as carrier, nickel, molybdenum and/or tungsten are active ingredient, and basic metal is auxiliary agent; The second Hydrobon catalyst: a kind of metal load type catalyst, take aluminum oxide as carrier, nickel, cobalt, tungsten are active ingredient, promotor is the arbitrary element in magnesium, zinc, iron, calcium.
Summary of the invention
The object of the present invention is to provide a kind of pre-hydrotreatment method of reforming feedstocks, particularly a kind of pretreatment process of the hydrogenation for raw materials for catalytic reforming device.The method only need be carried out a hydrotreatment, invest low, catalyst hydrogenation activity and good stability, but operational condition wide ranges.
The method of reformer feed pre-hydrotreating of the present invention comprises: catalytic reforming raw material enters the reactor that hydrotreating catalyst is housed under hydrogen atmosphere, the pretreatment technology condition is: the reaction temperature in is 200～320 ℃ (preferably 220～300 ℃), working pressure is greater than 2.4MPa (preferably 2.4～3.0MPa), and fresh feed oil volume air speed is 4～12h
-1(preferred 6～10h
-1), hydrogen to oil volume ratio is 50～300 (preferably 60～200); Described hydrotreating catalyst is cobalt-molybdenum series catalyst, take silicon-containing alumina as carrier, cobalt, molybdenum are active ingredient, boron and basic metal and/or alkaline-earth metal, as auxiliary agent, in catalyst weight, contain molybdenum oxide 10～20wt%, cobalt oxide 1～8wt%, boron oxide compound 0.5～5wt%, basic metal and/or alkaline earth metal oxide 1～5wt%, silicon oxide 6～26wt%.Specific surface area of catalyst 220～300m
2/ g, pore volume 0.55～0.75ml/g, wherein the presoma of silicon-containing alumina carrier is the pseudo-boehmite containing amorphous aluminum silicide, it is by first preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries, by above-mentioned amorphous aluminum silicide slurries and pseudo-boehmite slurries according to the ratio of silica content 5～40wt% mixed, aging, digestion time is 10～30min, then through the last handling process that comprises filtration, washing, drying, obtains.If silicon-containing alumina carrier prepared by other method can not reach effect of the present invention even if same catalyzer forms.
In reactor, mainly carry out hydrogenating desulfurization, denitrogenation and olefin saturation.Reactor insulation fix bed reactor preferably in the present invention.
Catalytic reforming raw material comprises virgin naphtha, catalytically cracked gasoline or both mixtures.The weight ratio of described catalytically cracked gasoline and virgin naphtha is 10: 90～50: 50.
The present invention also provides a kind of catalyzer that is applicable to the catalytic reforming raw material pre-hydrotreating, uses this catalyzer can obtain excellent especially desulfurization, denitrogenation and olefin saturated effect.
Support of the catalyst can add one or more in boron, basic metal, alkaline-earth metal before extruded moulding.The method of recommend adoption one of the following obtains:
Method one: will be containing 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: the silicon-containing alumina carrier is by add one or more acquisitions in basic metal, alkaline-earth metal, boron before extruded moulding.As will be containing precursor, nitric acid, the water mixer kneader of pseudo-boehmite and basic metal, alkaline-earth metal and/or the boron of amorphous aluminum silicide, extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h, obtain support of the catalyst.
Method three: after adding nitric acid, water to be mediated in containing the pseudo-boehmite of amorphous aluminum silicide, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, then flood the precursor solutions such as soluble salt of basic metal, alkaline-earth metal and/or boron, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h, make support of the catalyst.
Hydrotreating catalyst is that the preparation method that cobalt-molybdenum series catalyst can adopt the present invention to recommend obtains: will impregnated on carrier containing the aqueous solution of molybdenum and cobalt soluble salt, after drying at 300～500 ℃ of lower roasting 3～6h.
Basic metal and/or alkaline-earth metal and auxiliary agent boron all can add when preparing carrier, also can be after the carrier moulding, before cobalt, molybdenum add, be added in advance in carrier, to containing the aqueous solution of cobalt, molybdenum soluble salt, impregnated on the silicon-containing alumina carrier again, at 300～500 ℃ of lower roasting 3～6h, make catalyzer after drying.Can also be when dipping cobalt, molybdenum, with cobalt, molybdenum, add simultaneously, the aqueous solution that soon basic metal, alkaline-earth metal and/or boron will be added to containing cobalt, molybdenum soluble salt impregnated on the silicon-containing alumina carrier, after drying, at 300～500 ℃ of lower roasting 3～6h, makes catalyzer.
Can be to add nitric acid, water to carry out mixer kneader containing in the pseudo-boehmite of amorphous aluminum silicide more specifically, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, then flood the soluble salt solution of basic metal, alkaline-earth metal and/or phosphoric, 80～120 ℃ of oven dry, 400～700 ℃ of roasting 4～6h, with the dipping of the aqueous solution containing molybdenum, cobalt soluble salt, after drying, at 300～500 ℃ of lower roasting 3～6h, make catalyzer again.
The most outstanding characteristics of hydrotreating catalyst that pre-hydrotreatment method of reforming feedstocks of the present invention is used are that the presoma of the silicon-containing alumina carrier that catalytic amount is used is the pseudo-boehmite containing amorphous aluminum silicide, having selected it is to mix with first preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries, aging, and include filtration, dry last handling process obtains, the mixing process of these amorphous aluminum silicide slurries and pseudo-boehmite slurries, both be different from simple and mechanical mixing of two kinds of powders of amorphous aluminum silicide and pseudo-boehmite, it not again the structure of amorphous aluminum silicide coated alumina type.By two bursts of mixing of materials, one side amorphous aluminum silicide and pseudo-boehmite interaction; On the other hand, also be accompanied by a small amount of free aluminum ion and the reaction between silicate ion.
The present invention also provides a kind of preparation method of the pseudo-boehmite containing amorphous aluminum silicide, it is characterized in that amorphous aluminum silicide slurries and pseudo-boehmite slurries stream mix or a kind of material is joined in another kind of material and mixes, after mixing, aging 10～30min, filter, wash to sodium ions content and be less than 0.5wt%, under 80～120 ℃, dry 2～20h, obtain the pseudo-boehmite containing 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 finally made meets requirement of the present invention.
Preparation process of pseudoboehmite containing amorphous aluminum silicide provided by the invention comprises the preparation of amorphous aluminum silicide slurries and the preparation of pseudo-boehmite slurries, and these two kinds of slurries are mixed, the mixing of two kinds of slurries can adopt and flow and mixes or a kind of slurries are joined in another kind of slurries and mixed, then aging, more after filtration, washing, the last handling process such as dry obtain the pseudo-boehmite containing amorphous aluminum silicide.When aging, pH value of solution is preferably 9.0～10.5, 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, as the preparation of pseudo-boehmite slurries can adopt existing nitrate method or carborization.
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, be added in plastic cans, controls 15～50 ℃ of plastic cans temperature.
(b) compound concentration is 50～200gSiO
2The silicon-containing compound solution of/L, join silicon-containing compound solution in the solution of (a), controls pH value 11.5～13.
(c) low whipping speed is greater than under the condition of 250r/min, passes into continuously the carbon dioxide that concentration is greater than 20v%, controls the flow of carbon dioxide at 1～10Nm
3/ h, with time 20～40min, control endpoint pH 7.5～9.5 in control, and neutralization finishes.
(d), in pH value 7.5～9.5, solution 5～20min prepared by aging under the condition that temperature is 25～40 ℃ (c), obtain the amorphous aluminum silicide slurries.
Amorphous aluminum silicide slurries of the present invention are preferably with carbon dioxide process preparation, and silicon-containing compound can be water glass, silicon sol, water glass preferably, and concentration of sodium silicate is counted 50～200gSiO with silicon oxide
2/ L, be preferably 80～120gSiO
2/ L; The concentration of sodium metaaluminate or sodium aluminate solution is counted 10～150gAl with aluminum oxide
2O
3/ L, be preferably 35～110gAl
2O
3/ L; Digestion time preferably is controlled at 5～15min; Control silica alumina ratio 40～60wt% in 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 plastic cans, intermittence or continuous mode to pass into carbon dioxide through plastic, the aging pseudo-boehmite slurries that obtain.The concentration of sodium metaaluminate or sodium aluminate solution is 20～150gAl
2O
3/ L; The concentration of carbonic acid gas is greater than 20v%, is preferably between 40～100v%, and the flow of carbon dioxide is 1～10Nm
3/ h; 20～65 ℃ of plastic temperature, best 30～45 ℃; Plastic endpoint pH 9.0～10.5; Plastic and digestion time preferably are no more than 40min altogether, with 25～35min, are advisable.
In the preparation process of pseudo-boehmite slurries of the present invention, plastic terminal pH preferably is controlled at 9.0～10.5, the pH value was lower than 9.0 o'clock, the pseudo-boehmite formed easily and reaction of sodium bicarbonate generate a sodium stone structure, the silk sodium stone generated is a kind of insoluble salt, hinder the washing of sodium ion, likely affected the use properties of aluminum oxide as carrier.
Pseudo-boehmite best surfaces acidic site containing amorphous aluminum silicide prepared by the present invention be take the weak acid position as main.
The pseudo-boehmite containing amorphous aluminum silicide that the present invention selects, have the high acidity of amorphous aluminum silicide, the characteristic of high-specific surface area, contains the advantage of pseudo-boehmite simultaneously, overcome the poor problem of amorphous aluminum silicide moulding.The aluminum oxide containing amorphous aluminum silicide of preparation is specially adapted to do the carrier of hydrogenation catalyst.
Hydrotreating catalyst provided by the invention contains basic metal and/or alkaline-earth metal, can change the acid-basicity on support of the catalyst surface, is conducive to reduce the deposition of carbonaceous in hydrogenation process, colloid, thus the work-ing life of extending catalyst.The quantity that adds low, the middle intensity acid site that can improve catalyzer of auxiliary agent boron, also effectively stoped the inactivation of catalyzer.
Pre-hydrotreatment method of reforming feedstocks of the present invention has the following advantages:
1, the inventive method analoging industrial device, adopt insulation fix bed reactor, is conducive to the popularization to full scale plant.
2, the inventive method only need be carried out a hydrotreatment, and energy consumption is low, simple to operate and turndown ratio is large.
While 3, using the inventive method, adopt specific hydrotreating catalyst, hydrogenation activity and desulfurization, nitrogen removal performance are high, chemical stability and Heat stability is good, the strong and long service life of anti-coking performance.
4, use and the invention provides method, can under the low pressure condition, process the raw materials for catalytic reforming device that high sulfur-bearing is nitrogenous and olefin(e) centent is high, for catalytic reforming unit provides sulphur, nitrogen content, all be less than the acceptable material of 0.5 μ g/g.
Embodiment
Kaolinite Preparation of Catalyst agents useful for same source:
Ammonium molybdate: Shanghai gelatinizing factory
Cobaltous diacetate: Shanghai reagent two factories
Industry amorphous aluminum silicide: Zibo safe photoinitiator chemical company limited, SiO
2Content 45%.
Industry pseudo-boehmite: Zibo Wanlin Chemical Technology Co., Ltd.
Analytical procedure:
Oil distillation: adopt petroleum products test method SYB-2110-60 to measure;
Arsenic: adopt the DV-4300 Atomic Emission SpectrometerAES to measure;
Sulphur: adopt the WK-2B Microcoulomb instrument to measure;
Nitrogen: adopt KY-3000N chemoluminescence azotometer 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 preparation of catalyzer 1～8 for embodiment:
The preparation of catalyzer 1:
Configuration 2L concentration is 100gAl
2O
3The sodium aluminate solution of/L is placed in plastic cans, controls the plastic cans temperature 45 C, under agitation condition, passes into 65v%CO
2The mixed gas of+35v% air, in gas mixture, the flow of carbonic acid gas is 3Nm
3/ h.Stop passing into mixed gas when the pH value reaches 10.0, then aging 20min obtains the pseudo-boehmite slurries.
Configuration 3L concentration is 80gAl
2O
3The sodium aluminate solution of/L is placed in plastic cans, then adds 2L80gSiO
2The sodium silicate solution of/L, control 30 ℃ of plastic cans temperature, passes into 60v%CO
2The mixed gas of+40v% air, CO in gas mixture
2Flow be 3Nm
3/ h, controlling endpoint pH is 9.0, aging 15min obtains the amorphous aluminum silicide slurries.
Under the condition constantly stirred, 2L amorphous aluminum silicide slurries are joined in 1L pseudo-boehmite slurries, control 35 ℃ of mixing temperatures, aging 15min, filtration washing is to Na
+Content is less than 0.5%, 120 ℃ of dry 10h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
Will be containing the pseudo-boehmite of amorphous aluminum silicide and boric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 550 ℃ of roasting 3h, then use the saturated impregnated carrier of Lithium Citrate de solution, 120 ℃ of oven dry, 550 ℃ of roasting 4h, obtain the alumina supporter of siliceous, boron and lithium.Cobaltous diacetate and ammonium molybdate jointly are dissolved in the water and make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 480 ℃ of roastings, obtain containing CoO 3.5wt%, MoO
315.5wt%, SiO
218.3wt%, B
2O
33.5wt%, Li
2The catalyzer 1 of O 3.0wt%.
The preparation of catalyzer 2:
The preparation of pseudo-boehmite slurries is with catalyzer 1.Configuration 2L concentration is 130gAl
2O
3The sodium aluminate solution of/L is placed in plastic cans, then adds 2L 100gSiO
2The sodium silicate solution of/L, control 30 ℃ of plastic cans temperature, passes into 60v%CO
2The mixed gas of+40v% air, CO in gas mixture
2Flow be 3Nm
3/ h, controlling endpoint pH is 9.0, aging 15min obtains the amorphous aluminum silicide slurries.
Under the condition constantly stirred, 2L amorphous aluminum silicide slurries are joined in 1L pseudo-boehmite slurries, control 30 ℃ of mixing temperatures, aging 20min, filtration washing is to Na
+Content is less than 0.5%, 120 ℃ of dry 15h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
Will be containing the pseudo-boehmite of amorphous aluminum silicide and boric acid, saltpetre, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 520 ℃ of roasting 4h, obtain the alumina supporter of siliceous, boron and potassium.Cobaltous diacetate and ammonium molybdate jointly are dissolved in the water and make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 400 ℃ of roasting 4h, obtain containing CoO 3.0wt%, MoO
317wt%, SiO
223wt%, B
2O
32.5wt%, K
2The catalyzer 2 of O 1.5wt%.
The preparation of catalyzer 3:
Configuration 2L concentration is 100gAl
2O
3The sodium aluminate solution of/L is placed in plastic cans, controls 40 ℃ of plastic cans temperature, under agitation condition, passes into 60v%CO
2The mixed gas of+40v% air, in gas mixture, the flow of carbonic acid gas is 5Nm
3/ h.Stop passing into mixed gas when the pH value reaches 10.0, then aging 25min obtains the pseudo-boehmite slurries.
Configuration 2L concentration is 130gAl
2O
3The sodium aluminate solution of/L is placed in plastic cans, then adds 2L 80gSiO
2The sodium silicate solution of/L, control 20 ℃ of temperature of reaction, passes into 50v%CO
2The mixed gas of+50v% air, CO in mixed gas
2Flow be 6Nm
3/ h, controlling endpoint pH is 9.5, aging 18min obtains the amorphous aluminum silicide slurries.
Under the condition constantly stirred, 1L pseudo-boehmite slurries and 3L amorphous aluminum silicide slurries stream are joined in plastic cans, control 40 ℃ of mixing temperatures, aging 15min, filtration washing is to Na
+Content is less than 0.5%, 120 ℃ of dry 12h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
Will be containing the pseudo-boehmite of amorphous aluminum silicide and boric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 600 ℃ of roasting 4h, obtain siliceous and alumina supporter boron.Cobaltous diacetate, ammonium molybdate and magnesium nitrate jointly are dissolved in the water and make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 500 ℃ of roasting 4h, obtain containing CoO 4.0wt%, MoO
315wt%, SiO
222wt%, B
2O
3The catalyzer 3 of 2.0wt%, MgO 3.0wt%.
The preparation of catalyzer 4:
The preparation method of amorphous aluminum silicide slurries and pseudo-boehmite slurries is with catalyzer 3.
Under the condition constantly stirred, 1.5L pseudo-boehmite slurries and 1.6L amorphous aluminum silicide slurries stream are joined in plastic cans, control 45 ℃ of mixing temperatures, aging 20min, filtration washing is to Na
+Content is less than 0.5%, 110 ℃ of dry 15h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
Will be containing the pseudo-boehmite of amorphous aluminum silicide and boric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 4h, then use the saturated impregnated carrier of mixing solutions of saltpetre and strontium nitrate, 120 ℃ of oven dry, 650 ℃ of roasting 4h, obtain the alumina supporter of siliceous, boron, potassium and strontium.Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate jointly are dissolved in the water and make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 460 ℃ of roasting 4h, obtain containing CoO 4.0wt%, MoO
316.5wt%, SiO
214.7wt%, B
2O
33.5wt%, K
2The catalyzer 4 of O 0.5wt%, SrO 2.5wt%.
The preparation of catalyzer 5:
Configuration 2L concentration is 75gAl
2O
3The sodium aluminate solution of/L, be placed in plastic cans, and controlling the plastic cans temperature is 50 ℃, and under the condition constantly stirred, passing into concentration is 80v%CO
2The mixed gas of+20v% air, in gas mixture, the flow of carbonic acid gas is 4Nm
3/ h stops passing into mixed gas when the pH value reaches 10.0, and aging 20min obtains the pseudo-boehmite slurries.
Configuration 3L concentration is 80gAl
2O
3The sodium aluminate solution of/L is placed in plastic cans, then adds 2L70gSiO
2The sodium silicate solution of/L, control 30 ℃ of temperature of reaction, passes into 60v%CO
2The mixed gas of+40v% air, CO in gas mixture
2Flow be 5Nm
3/ h, controlling endpoint pH is 9.5, aging 18min obtains the amorphous aluminum silicide slurries.
Under the condition constantly stirred, 2L pseudo-boehmite slurries and 1L amorphous aluminum silicide slurries stream are joined in plastic cans, control 60 ℃ of mixing temperatures, aging 10min, filtration washing is to Na
+Content is less than 0.5%, 120 ℃ of dry 10h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
Will be containing the pseudo-boehmite of amorphous aluminum silicide and boric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 460 ℃ of roasting 4h, then use the saturated impregnated carrier of liquor kalii acetici, 120 ℃ of oven dry, 550 ℃ of roasting 4h, obtain the alumina supporter of siliceous, boron and potassium.Cobaltous diacetate and ammonium molybdate jointly are dissolved in the water and make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 450 ℃ of roasting 4h, obtain containing CoO 4.0wt%, MoO
318wt%, SiO
27.5wt%, B
2O
33.0wt%, K
2The catalyzer 5 of O 1.5wt%.
The preparation of catalyzer 6:
Configuration 2L concentration is 78gAl
2O
3The sodium aluminate solution of/L, be placed in plastic cans, and controlling the plastic cans temperature is 50 ℃, and under the condition constantly stirred, passing into concentration is 80v%CO
2The mixed gas of+20v% air, in gas mixture, the flow of carbonic acid gas is 4Nm
3/ h stops passing into mixed gas when the pH value reaches 10.0, and aging 20min obtains the pseudo-boehmite slurries.
Configuration 3L concentration is 100gAl
2O
3The sodium aluminate solution of/L is placed in plastic cans, then adds 2L 60gSiO
2The sodium silicate solution of/L, control 30 ℃ of temperature of reaction, passes into 60v%CO
2The mixed gas of+40v% air, CO in gas mixture
2Flow be 5Nm
3/ h, controlling endpoint pH is 9.5, aging 18min obtains the amorphous aluminum silicide slurries.
Under the condition constantly stirred, 2L pseudo-boehmite slurries and 2L amorphous aluminum silicide slurries stream are joined in plastic cans, control 60 ℃ of mixing temperatures, aging 10min, filtration washing is to Na
+Content is less than 0.5%, 120 ℃ of dry 8h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
Will be containing the pseudo-boehmite of amorphous aluminum silicide and boric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 460 ℃ of roasting 4h, then use the saturated impregnated carrier of strontium nitrate solution, 120 ℃ of oven dry, 500 ℃ of roasting 4h, obtain the alumina supporter of siliceous, boron and strontium.Cobaltous diacetate and ammonium molybdate jointly are dissolved in the water and make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 450 ℃ of roasting 4h, obtain containing CoO 2.5wt%, MoO
314wt%, SiO
211.9wt%, B
2O
3The catalyzer 6 of 2.4wt%, SrO 0.8wt%.
The preparation of catalyzer 7:
The preparation of amorphous aluminum silicide slurries and pseudo-boehmite slurries is with catalyzer 1.
Under the condition constantly stirred, 2L amorphous aluminum silicide slurries are joined in 2L pseudo-boehmite slurries, control 45 ℃ of mixing temperatures, aging 15min, filtration washing is to Na
+Content is less than 0.5%, 120 ℃ of dry 10h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
Will be containing the pseudo-boehmite of amorphous aluminum silicide and boric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 3h, then use the saturated impregnated carrier of Lithium Citrate de solution, 120 ℃ of oven dry, 500 ℃ of roasting 4h, obtain the alumina supporter of siliceous, boron and lithium.Cobaltous diacetate and ammonium molybdate jointly are dissolved in the water and make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 480 ℃ of roastings, obtain containing CoO 4.0wt%, MoO
317.5wt%, SiO
213.2wt%, B
2O
32.5wt%, Li
2The catalyzer 7 of O 2.0wt%.
The preparation of catalyzer 8:
The preparation of amorphous aluminum silicide slurries and pseudo-boehmite slurries is with catalyzer 6.
Under the condition constantly stirred, 2L pseudo-boehmite slurries and 1L amorphous aluminum silicide slurries stream are joined in plastic cans, control 60 ℃ of mixing temperatures, aging 10min, filtration washing is to Na
+Content is less than 0.5%, 120 ℃ of dry 8h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
Will be containing the pseudo-boehmite of amorphous aluminum silicide and boric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 450 ℃ of roasting 4h, then use the saturated impregnated carrier of magnesium nitrate solution, 120 ℃ of oven dry, 550 ℃ of roasting 4h, obtain the alumina supporter of siliceous, boron and magnesium.Cobaltous diacetate and ammonium molybdate jointly are dissolved in the water and make steeping fluid, be impregnated on the 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 4h, obtain containing CoO 5.5wt%, MoO
316.5wt%, SiO
27.3wt%, B
2O
3The catalyzer 8 of 3.0wt%, MgO 2.0wt%.
Embodiment is as shown in table 1 with the physico-chemical property of catalyzer 1～8.
Stock oil character is in Table 2.
The physico-chemical property of catalyzer 1～8 for table 1 embodiment
Table 2 stock oil character
| Project | Stock oil 1 | Stock oil 2 | Stock oil 3 | Stock oil 4 |
| Density (g/ml) | 0.724 | 0.725 | 0.736 | 0.743 |
| Boiling range (℃) | 60～180 | 62～180 | 60～178 | 60～182 |
| Bromine valency * 10 -2(g/g) | 2.12 | 2.20 | 17.4 | 19.6 |
| Sulphur content (μ g/g) | 180 | 182 | 245 | 302 |
| Nitrogen content (μ g/g) | 3.46 | 4.02 | 7.43 | 9.86 |
| Arsenic content (ng/g) | 13 | 15 | 18 | 20 |
Annotate: raw material 1,2 is virgin naphtha; Raw material 3 is catalytically cracked gasoline and virgin naphtha mixture, and wherein the weight ratio of catalytically cracked gasoline and virgin naphtha is 20: 80; Raw material 4 is catalytically cracked gasoline and virgin naphtha mixture, and wherein the weight ratio of catalytically cracked gasoline and virgin naphtha is 35: 65.
Embodiment 1
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, uses catalyzer 1.First carry out the sulfuration of catalyzer: dithiocarbonic anhydride is joined in hexanaphthene to the vulcanized oil that is made into sulphur content 1000 μ g/g left and right, reactor is warmed up to 240 ℃ to start into vulcanized oil, pressure 2.5Mpa, vulcanized oil volume space velocity 3.0h
-1, hydrogen/vulcanized oil volume ratio 300: 1, then the temperature rise rate with 10 ℃/h is warmed up to 350 ℃, maintains 25h, completes the sulfidizing to catalyzer.
Sulfidizing switches to stock oil 1,220 ℃ of temperature of reaction, reaction pressure 2.4MPa, liquid air speed 11h after finishing
-1, hydrogen to oil volume ratio 70, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 2
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, uses catalyzer 2.The catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing switches to stock oil 2,240 ℃ of temperature of reaction, reaction pressure 2.5MPa, liquid air speed 10h after finishing
-1, hydrogen to oil volume ratio 80, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 3
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, uses catalyzer 3.The catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing switches to stock oil 3,280 ℃ of temperature of reaction, reaction pressure 2.8MPa, liquid air speed 8h after finishing
-1, hydrogen to oil volume ratio 150, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 4
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, uses catalyzer 4.The catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing switches to stock oil 4,300 ℃ of temperature of reaction, reaction pressure 3.0MPa, liquid air speed 6h after finishing
-1, hydrogen to oil volume ratio 180, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 5
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, uses catalyzer 5.The catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing switches to stock oil 1,220 ℃ of temperature of reaction, reaction pressure 2.4MPa, liquid air speed 10h after finishing
-1, hydrogen to oil volume ratio 80, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 6
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, uses catalyzer 6.The catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing switches to stock oil 2,240 ℃ of temperature of reaction, reaction pressure 2.6MPa, liquid air speed 12h after finishing
-1, hydrogen to oil volume ratio 100, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 7
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, uses catalyzer 7.The catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing switches to stock oil 3,260 ℃ of temperature of reaction, reaction pressure 2.8MPa, liquid air speed 8h after finishing
-1, hydrogen to oil volume ratio 200, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 8
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, uses catalyzer 8.The catalyst vulcanization treatment process is with embodiment 1.
Sulfidizing switches to stock oil 2,250 ℃ of temperature of reaction, reaction pressure 2.6MPa, liquid air speed 10h after finishing
-1, hydrogen to oil volume ratio 90, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Comparative Examples 1
It is the silica-alumina powder that this Comparative Examples is used the presoma of support of the catalyst, according to the described method preparation of embodiment in CN1267187C 3; The preparation method of catalyzer and composition are with catalyzer 3 for embodiment.
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, and the catalyst vulcanization treatment process is with embodiment 1; Pre-hydrotreating, with embodiment 3, the results are shown in Table 3.
Comparative Examples 2
This Comparative Examples is used the presoma of support of the catalyst according to the described method preparation of embodiment in CN1074303C 1; The preparation method of catalyzer and composition are with catalyzer 4 for embodiment.
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, and the catalyst vulcanization treatment process is with embodiment 1; Pre-hydrotreating, with embodiment 4, the results are shown in Table 3.
Comparative Examples 3
This Comparative Examples is used the presoma of support of the catalyst according to the described method preparation of embodiment in CN1306977C 4; The preparation method of catalyzer and composition are with catalyzer 2 for embodiment.
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, and the catalyst vulcanization treatment process is with embodiment 1; Pre-hydrotreating, with embodiment 2, the results are shown in Table 3.
Comparative Examples 4
The catalyzer that this Comparative Examples is used is according to the described method preparation of embodiment in CN100487085C 3, and catalyzer consists of: CoO 2.5wt%, MoO
314wt%, B
2O
32.4wt%, SrO 0.8wt%, TiO
211.9wt%, WO
31.2wt%.
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, and the catalyst vulcanization treatment process is with embodiment 1; Pre-hydrotreating, with embodiment 6, the results are shown in Table 3.
Comparative Examples 5
It is industrial amorphous aluminum silicide (SiO that this Comparative Examples is used the presoma of support of the catalyst
2Content 45%); The preparation method of catalyzer is with catalyzer 3 for embodiment.Catalyzer consists of: CoO 4.0wt%, MoO
315wt%, SiO
234.2wt%, B
2O
32.0wt%, MgO 3.0wt%.
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, and the catalyst vulcanization treatment process is with embodiment 1; Pre-hydrotreating, with embodiment 3, the results are shown in Table 3.
Comparative Examples 6
It is industrial pseudo-boehmite that this Comparative Examples is used the presoma of support of the catalyst; The preparation method of catalyzer is with catalyzer 1 for embodiment, the oxygen-free SiClx of this catalyzer, and all the other form with catalyzer 1.
The pre-hydrotreating reactor adopts the heat-insulating fixed bed, and the catalyst vulcanization treatment process is with embodiment 1; Pre-hydrotreating, with embodiment 1, the results are shown in Table 3.
As shown in Table 3, the present invention contains hydrogenation catalyst prepared by the pseudo-boehmite of amorphous aluminum silicide by employing reformer feed is carried out to pre-hydrotreating, sulphur content in hydrogenated products<0.5 μ g/g, and nitrogen content<0.5 μ g/g, meet catalytic reforming unit charging requirement; For processing the reformer feed that high sulfur-bearing is nitrogenous and olefin(e) centent is high, can all be less than the acceptable material of 0.5 μ g/g for catalytic reforming unit provides sulphur, nitrogen content equally simultaneously.
Table 3 embodiment 1～8 and Comparative Examples 1～6 pre-hydrotreating data
Claims (17)
1. a pre-hydrotreatment method of reforming feedstocks, it is characterized in that the method comprises: catalytic reforming raw material enters the reactor that hydrotreating catalyst is housed under hydrogen atmosphere, the pretreatment technology condition is: the reaction temperature in is 200～320 ℃, working pressure is greater than 2.4MPa, and fresh feed oil volume air speed is 4～12h
-1, hydrogen to oil volume ratio is 50～300; Described hydrotreating catalyst is cobalt-molybdenum series catalyst, take silicon-containing alumina as carrier, cobalt, molybdenum are active ingredient, and one or both in basic metal, alkaline-earth metal and boron are as auxiliary agent, in catalyst weight, contain molybdenum oxide 10～20wt%, cobalt oxide 1～8wt%, boron oxide compound 0.5～5wt%, basic metal and/or alkaline earth metal oxide 1～5wt%, silicon oxide 6～26wt%, specific surface area of catalyst 220～300m
2/ g, pore volume 0.55～0.75ml/g, wherein the presoma of silicon-containing alumina carrier is the pseudo-boehmite containing amorphous aluminum silicide, it is by first preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries, by above-mentioned amorphous aluminum silicide slurries and pseudo-boehmite slurries according to the ratio of silica content 5～40wt% mixed, aging, digestion time is 10～30min, then through the last handling process that comprises filtration, washing, drying, obtains the pseudo-boehmite containing amorphous aluminum silicide.
2. pre-hydrotreatment method of reforming feedstocks according to claim 1, it is characterized in that reacting temperature in is 220～300 ℃.
3. pre-hydrotreatment method of reforming feedstocks according to claim 1, is characterized in that working pressure is 2.4～3.0MPa.
4. pre-hydrotreatment method of reforming feedstocks according to claim 1, is characterized in that fresh feed oil volume air speed is 6～10h
-1.
5. pre-hydrotreatment method of reforming feedstocks according to claim 1, is characterized in that hydrogen to oil volume ratio is 60～200.
6. pre-hydrotreatment method of reforming feedstocks according to claim 1, it is characterized in that: described catalytic reforming raw material is virgin naphtha, catalytically cracked gasoline or both mixtures.
7. pre-hydrotreatment method of reforming feedstocks according to claim 6, it is characterized in that: described catalytic reforming raw material is virgin naphtha, both mixtures of catalytically cracked gasoline, and the weight ratio of catalytically cracked gasoline and virgin naphtha is 10:90～50:50.
8. pre-hydrotreatment method of reforming feedstocks according to claim 1, it is characterized in that the pseudo-boehmite containing amorphous aluminum silicide is by amorphous aluminum silicide slurries and pseudo-boehmite slurries are also flowed and mix or a kind of slurries are joined in another kind of slurries and mix, after having mixed, when aging, pH value of solution is 9.0～10.5.
9. according to the described pre-hydrotreatment method of reforming feedstocks of claim 1 or 8, it is characterized in that when aging that temperature is 20～65 ℃.
10. according to the described pre-hydrotreatment method of reforming feedstocks of claim 1 or 8, 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 plastic cans, controls 15～50 ℃ of plastic cans temperature;
(b) compound concentration is 50～200gSiO
2The silicon-containing compound solution of/L, join in the sodium metaaluminate or sodium aluminate solution liquor of (a), controls pH value 11.5～13;
(c) low whipping speed is greater than under the condition of 250r/min, passes into continuously the carbon dioxide that concentration is greater than 20v%, controls the flow of carbon dioxide 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 under the condition that temperature is 25～40 ℃ (c) 5～20min, obtain the amorphous aluminum silicide slurries.
11. according to the described pre-hydrotreatment method of reforming feedstocks of claim 1 or 8, it is characterized in that the pseudo-boehmite slurries obtain by following method: sodium metaaluminate or sodium aluminate solution are placed in to plastic cans, intermittence or continuous mode to pass into carbon dioxide plastic, 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; 20～65 ℃ of plastic temperature; Plastic endpoint pH 9.0～10.5, be less than 40min with time and digestion time sum in plastic.
12. pre-hydrotreatment method of reforming feedstocks according to claim 1, is characterized in that cobalt-molybdenum series catalyst is by impregnated in containing the aqueous solution of cobalt, molybdenum soluble salt on the silicon-containing alumina carrier, and make at 300～500 ℃ of lower roasting 3～6h after drying.
13. pre-hydrotreatment method of reforming feedstocks according to claim 12, it is characterized in that the silicon-containing alumina carrier is by will be containing 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 make.
14. pre-hydrotreatment method of reforming feedstocks according to claim 12, it is characterized in that the silicon-containing alumina carrier is by will be containing the pseudo-boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, add one or more in basic metal, alkaline-earth metal, boron, then extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h make.
15. pre-hydrotreatment method of reforming feedstocks according to claim 12, it is characterized in that cobalt-molybdenum series catalyst is by being added in advance in the silicon-containing alumina carrier by basic metal, alkaline-earth metal and/or boron before cobalt, molybdenum add, impregnated in again the aqueous solution containing cobalt, molybdenum soluble salt, make at 300～500 ℃ of lower roasting 3～6h after drying.
16. pre-hydrotreatment method of reforming feedstocks according to claim 12, it is characterized in that cobalt-molybdenum series catalyst is that the aqueous solution by basic metal, alkaline-earth metal and/or boron being added to containing cobalt, molybdenum soluble salt impregnated on the silicon-containing alumina carrier, makes at 300～500 ℃ of lower roasting 3～6h after drying.
17. pre-hydrotreatment method of reforming feedstocks according to claim 15, it is characterized in that cobalt-molybdenum series catalyst is by containing in the pseudo-boehmite of amorphous aluminum silicide, adding nitric acid, water to carry out mixer kneader, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, then flood the soluble salt solution of basic metal, alkaline-earth metal and/or boron, 80～120 ℃ of oven dry, 400～700 ℃ of roasting 4～6h, impregnated in again the aqueous solution containing cobalt, molybdenum soluble salt, make at 300～500 ℃ of lower roasting 3～6h after drying.
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| CN108262047B (en) * | 2016-12-30 | 2021-03-09 | 中国石油天然气股份有限公司 | Nickel-molybdenum series hydrogenation catalyst and preparation method thereof |
| CN110129093A (en) * | 2019-05-21 | 2019-08-16 | 山东京博石油化工有限公司 | A kind of pre-hydrotreating reaction system |
| CN111774048A (en) * | 2020-07-13 | 2020-10-16 | 沈阳三聚凯特催化剂有限公司 | Method for preparing alumina carrier, reforming protective agent and preparation method thereof |
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