CN106669752A - Spherical hydrogenation catalyst composition and preparation method thereof - Google Patents
Spherical hydrogenation catalyst composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a spherical hydrogenation catalyst composition and a preparation method thereof. The spherical hydrogenation catalyst composition comprises a hydrogenation activity metal, an aid and an alumina support. The hydrogenation activity metal component is composed of one or more of Group VIB metals and Group VIII metals; the aid is one combination of I, II and III as follows: I is fluorine and phosphorus, II is fluorine and boron, III is fluorine, phosphorus and boron, and preferably fluorine, phosphorus and boron; and the rest is the alumina support. The hydrogenation activity metal concentration and aid concentration gradually increase from the center of the catalyst particle to the external surface; the specific area of the spherical hydrogenation catalyst composition is 200-250 m<2>/g, and the pore volume is 0.4-0.7 ml/g; and the spherical hydrogenation catalyst composition has the dual pore distribution, and the pore sizes are 10-15nm and 15-30nm. The preparation method comprises the following steps: adding ionic liquids with different molecular sizes and different aid element types in the gelling and kneading process, drying, and roasting to obtain the product. The pore structure and acidity distribution can be organically matched to enhance the overall performance of the catalyst; and thus, the catalyst has wide application prospects in high-desulfurization/denitrification reactions of inferior wax oil, residual oil and other raw materials.
Description
Technical field
The present invention relates to a kind of spherical hydrogenation catalyst composition and preparation method thereof, specifically a kind of active metal and auxiliary agent weight/mass percentage composition increase in gradient and hydrogenating catalyst composition with dual pore distribution and preparation method thereof.
Background technology
Containing sulphur, nitrogen, oxygen and metal impurities in crude oil and the distillate that obtains from crude oil.The presence of these impurity not only affects the stability of oil product, and can also discharge SO in useX、NOXEnvironment is polluted Deng pernicious gas.In the secondary processing process of oil product, the presence of sulphur, nitrogen, oxygen and metal impurities can make catalyst poisoning.Therefore, it is the significant process in oil product processing to remove above-mentioned impurity.Distillate hydrogenation process refers to that under uniform temperature and pressure, feedstock oil and hydrogen are contacted with catalyst, imurity-removal, and the process of aromatic hydrocarbons saturation.
At present, the hydrotreating almost all of petroleum refining industry adopts alumina support.Due to the irregular condensation of surface hydroxyl, alumina support is respectively provided with certain acidity, and these acid centres are easily caused hydro carbons condensation and form carbon deposit, cause catalyst to inactivate.The mink cell focus hydroprocessing processes of carbon deposit, the acid strong and weak directly decision catalyst of catalyst support surface are easily caused to be capable of the length of stable operation cycle especially for some.At present, hydrotreating catalyst is with aluminum oxide or the aluminum oxide containing one or more other elements such as Si, Ti, P, B, F etc. as carrier.In catalyst preparation process, above-mentioned element can be introduced into system in different phase, its object is to the acidity of regulating catalyst, and improve the interaction between active component and carrier.The preparation method of conventional catalyst, the concentration distribution of auxiliary agent is often than more uniform in its particle.At present, the document report with regard to assistant concentration in uneven distribution is less.
CN101927169A the present invention relates to a kind of active metal component concentration in gradient increase distribution hydrogenation catalyst and preparation method, with Al2O3Or contain SiO2、TiO2、ZrO2Al2O3As carrier, VIB and/or group VIII metal compound and deionized water or ammoniacal liquor are mixed and made into metal impregnation liquid, the method impregnated using saturation prepares hydrogenation catalyst；By the diluter VIB of preparation and/or group VIII metal solution or deionized water, during carrier impregnation, progressively add denseer metallic solution saturation impregnated carrier；Or by preparing the metallic solution of variable concentrations, be immersed in from low to high on carrier by metal impregnation concentration, it is dried 1～8 hour at 80～150 DEG C, roasting 2～6 hours in 300～650 DEG C of air；This catalyst has preferable desulfurization, denitrogenation, de- carbon residue activity and stability, prepares simple, manufacturing cost reduction, it is adaptable to mink cell focus field of hydrogenation.
CN201210462040.9 is specifically related to a kind of phosphorous, fluorine, the preparation method of the micro-spherical catalyst carrier of titanium.The method be first phosphorous contained amorphous silica-alumina dry glue, fluorine-contained amorphous silica-alumina dry glue are well mixed with titanium-containing amorphous silicon-aluminum dry gel after, again will mixing dry glue wetting, extruded moulding, Jing granulations, screening, be dried, the micro-spherical catalyst carrier of phosphorous, fluorine, titanium is made in roasting.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of spherical hydrogenation catalyst composition and preparation method thereof.Hydrogenation active metals and assistant concentration in the carbon monoxide-olefin polymeric gradually increase from the inside to the outside, and with dual pore distribution, pore structure and acid distribution organically cooperate, and improve the overall performance of catalyst, it is adaptable to hydrodesulfurization, the denitrification reaction of the raw material such as faulty wax oil, residual oil.
The spherical hydrogenation catalyst composition of the present invention, including hydrogenation active metals, auxiliary agent and alumina support；Described hydrogenation active metals component is one or more in vib metals and group VIII metal, and wherein vib metals are preferably W and/or Mo, and group VIII metal is preferably Co and/or Ni；On the basis of the weight of catalyst, vib metals oxide content is 5.0wt% ~ 30.0wt%, and preferably 10.0wt% ~ 15.0wt%, group VIII metal oxide content is 0.5wt% ~ 10.0wt%, preferably 1.0wt% ~ 10.0wt%；Auxiliary agent is the one kind in several combinations of following I, II and III：I- fluorine and phosphorus, II- fluorine and boron, III- fluorine, phosphorus and boron, preferred III- fluorine, phosphorus and boron；Auxiliary agent is calculated as 1.5% ~ 2.0% with element, and when auxiliary agent is I, fluorine accounts for the 50%～55% of auxiliary agent quality, and phosphorus accounts for the 45%～50% of auxiliary agent gross mass；When auxiliary agent is II, fluorine accounts for the 50%～55% of auxiliary agent quality, and boron accounts for the 45%～50% of auxiliary agent gross mass；When auxiliary agent is III, fluorine accounts for the 50%～55% of auxiliary agent total amount, and phosphorus accounts for the 30% ~ 35% of auxiliary agent total amount, and boron accounts for the 15%～20% of auxiliary agent total amount；Balance of alumina support；
Described hydrogenation active metals concentration gradually increases from catalyst granules center to outer surface, and the hydrogenation active metals concentration at the wherein 1/4R in catalyst granules, at 1/2R and at R meets following proportionate relationship：C1/4R：C1/2R：CR=1：1.5~2.0：2.5～3.0；Assistant concentration gradually increases from catalyst granules center to outer surface, at the wherein 1/4R in catalyst granules, the assistant concentration at 1/2R and at R meet following proportionate relationship：C1/4R：C1/2R：CR=1：2~4：3~5；Wherein R is the radius of the catalyst granules with spheric catalyst composition center as initial point；
200 ~ the 250m of specific surface area of described spherical hydrogenation catalyst composition2/ g, 0.4 ~ 0.7ml/g of pore volume, with dual pore distribution, aperture is 10 ~ 15nm and 15 ~ 30nm；The wherein pore size distribution of 10 ~ 15nm accounts for total pore volume 35% ~ 40%, and the pore size distribution of 15-30nm accounts for the 30% ~ 35% of total pore volume.
The preparation method of the spherical hydrogenation catalyst composition of the present invention, including following content：
（1）
The preparation of ionic liquid
By M1Respectively and M2、M3、M4Make ionic liquid I, II and III；
（2）The preparation of boehmite
Ionic liquid I is added during sodium aluminate solution and aluminum sulfate solution plastic, after cemented into bundles, carries out aging, then filtered, after being dried boehmite I is obtained；
Ionic liquid II is separately added into during sodium aluminate solution and aluminum sulfate solution plastic, after cemented into bundles, carries out aging, then filtered, after being dried boehmite II is obtained；
Ionic liquid III is separately added into during sodium aluminate solution and aluminum sulfate solution plastic, after cemented into bundles, carries out aging, then filtered, after being dried boehmite III is obtained；
（3）
The preparation of hydrogenation active metals solution
Prepare maceration extract I, II and III that hydrogenation active metals concentration gradually increases, in terms of oxide, the concentration of hydrogenation active metals is 36 ~ 50g/100ml in maceration extract I, the concentration of hydrogenation active metals is 60 ~ 75 g/100ml in maceration extract II, the concentration of hydrogenation active metals is 20 ~ 30 g/100ml for the concentration increasing degree of 85 ~ 110 g/100ml, wherein maceration extract I and II or maceration extract II and III in maceration extract III.Hydrogenation active metals by taking Mo and Ni as an example, MoO in maceration extract I3Concentration be 30～40g/100ml, the concentration of NiO is 6～10g/100ml；MoO in maceration extract II3Concentration be 45～55g/100ml, the concentration of NiO is 15～20g/100ml；MoO in maceration extract III3Concentration be 60～80g/100ml, the concentration of NiO is 25～30g/100ml.
（4）The preparation of spherical hydrogenation catalyst composition
Boehmite I is placed in disk forming machine and is sufficiently mixed, and Jing sprayers are sprayed onto the ionic liquid I aqueous solution and maceration extract I on the aluminum oxide in rotating disk, after blended contact, obtains spheric catalyst presoma I；
Boehmite II is sufficiently mixed with spheric catalyst presoma I in disk forming machine again, the Jing atomizers sprays ionic liquid II aqueous solution and maceration extract II, after blended contact, spheric catalyst presoma II；
Then boehmite III is sufficiently mixed with spheric catalyst presoma II in disk forming machine, the Jing atomizers sprays ionic liquid III aqueous solution and maceration extract III, after blended contact, obtain spheric catalyst presoma III, drying, obtains spherical hydrogenation catalyst composition after roasting.
In the inventive method, step（1）The M1For one or more in ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate ammonium hexafluorophosphate, sodium hexafluoro phosphate, Potassium Hexafluorophosphate etc., preferably ammonium hexafluorophosphate and/or tetrafluoro boric acid are pressed.
In the inventive method, step（1）Described M2It is one or more in the alkyl ammonium halide of 1 ~ 4 for carbon number, alkyl is preferably one or more in methyl, ethyl, the more preferably preferred chlorine of halogen, dimethy lammonium chloride and/or diethyl ammonium halide.
In the inventive method, step（1）Described M3It is one or more in the alkyl ammonium halide of 4 ~ 8 for carbon number, alkyl is preferably one or more in methyl, ethyl, propyl group, the preferred chlorine of halogen, more preferably halogenation triethyl ammonium, halogenation tetraethyl ammonium, ethyl ammonium halide.
In the inventive method, step（1）Described M4It is one or more in the alkyl ammonium halide of 8 ~ 12 for carbon number, it is preferred that one or more in halogenated methyl tri-n-butylamine, halogenation dimethyl di-n-butylamine, halogenation propyl group tri-n-butylamine, halogenation dipropyl di-n-butylamine, halogenated methyl puratized agricultural spray, halogenation dimethyl puratized agricultural spray, halogenation trimethyl puratized agricultural spray etc., one or more preferably in halogenated methyl puratized agricultural spray or halogenation dimethyl di-n-butylamine, the preferred chlorine of halogen.
In the inventive method, step（1）The preparation method of intermediate ion liquid I can be carried out generally by M using conventional method1And M2It is added to the water, reaction temperature is heated under agitation, isothermal reaction after reaction terminates, is cooled down, and centrifugation obtains ionic liquid I；Wherein M1With M2Mol ratio be 1：1～1：2, reaction condition is generally reaction temperature for 60～150 DEG C, preferably 70～100 DEG C, and the isothermal reaction time is 1～4h, preferably 1～2h.The preparation method and preparation condition of ionic liquid II and III is identical with ionic liquid I, by the M in said method2It is substituted for M3Or M4, that is, obtain ionic liquid II or ionic liquid III.
In the inventive method, step（2）The sodium aluminate solution can be carried out with aluminum sulfate solution plastic using conventional method, preferably with cocurrent plastic method.Gelation Conditions are generally：Reaction temperature is 50 ~ 80 DEG C, and pH value is 6.5 ~ 9.0, and the reaction time is 0.5 ~ 2.0 hour.Aging condition is as follows after plastic：Aging temperature is 50 ~ 80 DEG C, and pH value is 8.5 ~ 11.0, and ageing time is 0.1 ~ 1.0 hour., as 10 ~ 30g/100mL, the concentration that aluminum sulfate solution is counted with aluminum oxide is as 3 ~ 10g/100mL for the concentration that sodium aluminate solution used is counted with aluminum oxide.
In the inventive method, step（2）The addition of ionic liquid I, II and III is calculated with the amount of its auxiliary element for containing, auxiliary element in wherein ionic liquid I accounts for catalyst combination amount of substance for 0.2wt～0.45wt%, it is 0.55wt～0.9wt% that auxiliary element in ionic liquid II accounts for catalyst combination amount of substance, and the auxiliary element in ionic liquid III accounts for catalyst combination amount of substance for 0.95wt～1.35wt%.
In the inventive method, step（2）Described in baking temperature be 40～200 DEG C, preferably 60～120 DEG C；Drying time is 1～5 hour, preferably 1～3 hour.
In the inventive method, step（4）Described in maceration extract I, II and III the hydrogenation active metals amount that contained with it of addition calculating, hydrogenation active metals in wherein maceration extract I counted with oxide the quality for accounting for carbon monoxide-olefin polymeric as 8.5wt～10.0wt%, hydrogenation active metals in maceration extract II counted with oxide the quality for accounting for carbon monoxide-olefin polymeric as 15.0wt～18.0wt%, the hydrogenation active metals in maceration extract III counted with oxide the quality for accounting for carbon monoxide-olefin polymeric as 20wt～25wt%.
The concentration of the step 4 intermediate ion liquid I aqueous solution represents that its concentration is 8～15% with ionic liquid mass percent in aqueous；The concentration of the ionic liquid II aqueous solution is 15～20%；The concentration of the aqueous solution of ionic liquid III is 22 ~ 25%；The concentration difference of ionic liquid I and ionic liquid II is 3～5%；Ionic liquid II is 3～5% with the concentration difference of ionic liquid III.
In the inventive method, step（4）Described in the auxiliary element amount that contained with it of ionic liquid I, II and III addition calculating, it is 0.2wt～0.45wt% that auxiliary element in wherein ionic liquid I accounts for the quality of carbon monoxide-olefin polymeric, it is 0.55wt～0.9wt% that auxiliary element in ionic liquid II accounts for the quality of carbon monoxide-olefin polymeric, and it is 0.95wt～1.35wt% that the auxiliary element in ionic liquid III accounts for the quality of carbon monoxide-olefin polymeric.
In the inventive method, step（4）In preparing the disk forming machine rotating operation condition described in spheric catalyst presoma I, the inclination angle of rotating disk is 40～70o, preferably 40～60o；The rotating speed of rotating disk is 10～20rpm；Molding time of the material in rotating disk is 10～30min.
In the inventive method, step（4）In preparing the disk forming machine rotating operation condition described in spheric catalyst presoma II, the inclination angle of rotating disk is 40～70o, preferably 40～60o；The rotating speed of rotating disk is 10～20rpm；Molding time of the material in rotating disk is 10～30min.
In the inventive method, step（4）In preparing the disk forming machine rotating operation condition described in spheric catalyst presoma III, the inclination angle of rotating disk is 40～70o, preferably 40～60 o；The rotating speed of rotating disk is 10～20rpm；Molding time of the material in rotating disk is 10～30min.
In the inventive method, step（4）Method for preparing catalyst is known to technical staff.The condition of the drying and roasting is conventional, and for example, baking temperature is 60 DEG C～180 DEG C, and preferably 80 DEG C～150 DEG C, drying time is 0.5h～15.0h, preferably 1h～6h；Sintering temperature is 500 DEG C～700 DEG C, and roasting time is 0.5h～15.0h.
Spherical hydrogenation catalyst composition of the present invention is suitable for use as the inferior raw material hydrotreating catalyst such as wax oil, residual oil, is applied to wax oil, residual hydrogenation reaction.
Pore structure in the inventive method is measured using N2 adsorption and mercury injection method；Auxiliary agent and active metal distribution are measured using field emission scanning electron microscope.
Compared with prior art, the present invention has advantages below：
1st, this method adopts and different types of ionic liquid is added during plastic and kneading, there are different space sizes using different ionic liquid, so that prepared hydrogenation catalyst has dual pore passage structure, the property of inferior raw material is can adapt to, is well suited for for hydrogenation processes such as wax oil, residual oil.
2nd, pore structure, acid distribution and the Metal Distribution for targetedly adjusting spherical hydrogenation catalyst using the consumption of different ionic liquid, ionic liquid and hydrogenation active metals in this method is adjusted, i.e. pore size distribution is concentrated mainly on 10 ~ 15nm and 15 ~ 30nm；The auxiliary agents such as fluorine, boron, the phosphorus of middle content are modified 10 ~ 15nm ducts by the introducing of small molecular ion liquid and active metal；The introducing that the auxiliary agents such as fluorine, boron, the phosphorus of high-load and active metal pass through macromolecular ionic liquid III, modifies 15 ~ 30nm ducts, so makes it cooperate, so as to improve the combination property of hydrogenation catalyst.
3rd, the active metal and auxiliary element concentration in hydrogenating catalyst composition of the present invention increases in gradient distribution in spheric catalyst, catalyst surface acidity can be effectively improved, active metal utilization rate is improved, slow down the deactivation rate of catalyst in mink cell focus hydroprocessing processes, it is well suited as high desulfurization, denitrogenation, the strong hydrotreating catalyst of stability.
Specific embodiment
The preparation method of the hydrogenating catalyst composition of the present invention is described in more detail below by specific embodiment.Embodiment does not constitute the restriction of the scope of the present invention simply to the illustration of the specific embodiment of the inventive method, and the feed postition of auxiliary agent is one or more in various incorporation ways.
In the embodiment of the present invention and comparative example：Molybdenum oxide, basic nickel carbonate, phosphoric acid, nitric acid（Concentration is 65wt%）, citric acid（Concentration is 99wt%）Pure to analyze, sesbania powder is pure for chemistry, the production of Shenyang Li Cheng chemical reagent works；NaOH, aluminium hydroxide, aluminum sulfate, Yantai Heng Hui Chemical Co., Ltd.s；Ammonium tetrafluoroborate, sodium tetrafluoroborate, Wuhan sea Dehua work Development Co., Ltd；Alkyl dimethyl ammonium chloride, triethyl ammonium chloride, diethylammonium chloride, dimethyl benzene ammonium chloride, trimethylphenyl ammonium chloride, aminomethyl phenyl ammonium chloride, etamon chloride, Qingdao Golden Horse Chemical Co., Ltd..
Embodiment 1
Alkyl dimethyl ammonium chloride 300g, ammonium tetrafluoroborate 190g, pure water 450g, mixing is heated under agitation 80 DEG C, after constant temperature 1h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains ionic liquid I 300g, aqueous about 3.5wt%, yield 73wt%.
Triethyl ammonium chloride 400g, sodium hexafluoro phosphate 220g, pure water 450g, mixing is heated under agitation 90 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 450g of ionic liquid II, aqueous about 3.5wt%, yield 72wt%.
Trimethylphenyl ammonium chloride 500g, sodium hexafluoro phosphate 260g, pure water 450g, mixing is heated under agitation 90 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 550g of ionic liquid III, aqueous about 3.5wt%, yield 74wt%.
5g the and 2L distilled water of ionic liquid I is added in reactor, adjustment reaction temperature is 60 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 7.5, reaction 1h after, carry out it is aging, aging pH be 11, ageing time 30min, filter, 100 DEG C be dried 2h and obtain boehmite I.
10g the and 3L distilled water of ionic liquid II is added in reactor, adjustment reaction temperature is 70 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 8.0, reaction 1h after, carry out it is aging, aging pH be 11, ageing time 30min, filter, 100 DEG C be dried 2h and obtain boehmite II.
15g the and 3L distilled water of ionic liquid III is added in reactor, adjustment reaction temperature is 80 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 8.5, reaction 1h after, carry out it is aging, aging pH be 11, ageing time 30min, filter, 100 DEG C be dried 2h and obtain boehmite III.
Take 386g molybdenum oxides, 123g basic nickel carbonates are put into many mouthfuls of flasks, after adding a certain amount of deionized water, it is stirred until then vial matter be slowly added 86g phosphoric acid in pulpous state, it is slowly heated again after Deng initial action, kept for 90 DEG C～110 DEG C times of solution temperature be that 1h～3h. stops after heating, while hot filtering resulting solution, after filtering some insoluble impurity, the bottle green maceration extract I clarified is obtained, then to be added water and respectively obtain maceration extract II, III with certain proportion dilution maceration extract.The concentration of maceration extract I is MoO3：31g/100ml；NiO：7.2g/100ml；The concentration of maceration extract II is MoO3：48g/100ml；NiO：16.7g/100ml；The concentration of maceration extract III is MoO3：70g/100ml；NiO：28g/100ml.
The boehmite I of 120g is placed in disk forming machine and is sufficiently mixed, the inclination angle for adjusting rotating disk is 40o, and the rotating speed of rotating disk is 10rpm；On the boehmite I that the mixed aqueous solution of spray-dried mixed aqueous solution and 30ml maceration extracts I and 60g water by 5g ionic liquids I and 60g water is sprayed onto in rotating disk after blended contact, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma I of 0.1～0.5mm of diameter；
Spheric catalyst presoma I prepared by the boehmite II of 120g and above-mentioned steps is sufficiently mixed in disk forming machine, the inclination angle for adjusting rotating disk is 40o, and the rotating speed of rotating disk is 10rpm；Jing after blended contact on the aluminum oxide II that sprayer is spread across the mixed aqueous solution that the mixed aqueous solution and 42ml maceration extracts of 12g ionic liquids II and 60g water spray II and 60g water in rotating disk, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma II of 1.0～1.5mm of diameter；
Spheric catalyst presoma II prepared by the boehmite III of 120g and above-mentioned steps is sufficiently mixed in disk forming machine, the inclination angle for adjusting rotating disk is 40o, and the rotating speed of rotating disk is 10rpm；Jing after blended contact on the boehmite III that sprayer is sprayed onto the mixed aqueous solution of the mixed aqueous solution and 65ml maceration extracts III and 60g water of 20g ionic liquids III and 60g water in rotating disk, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma III of 1.0～1.5mm of diameter；Spheric catalyst presoma III is dried into 3h through 120 DEG C, after 500 DEG C of roasting 3h, required spheric catalyst is obtained, CT-1 is denoted as, property is listed in Table 1 below.
Embodiment 2
Diethylammonium chloride 250g, ammonium tetrafluoroborate 180g, pure water 400g, mixing is heated under agitation 90 DEG C, after constant temperature 1.5h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains ionic liquid I 260g, aqueous about 3.5wt%, yield 73wt%.
Triethyl ammonium chloride 300g, sodium hexafluoro phosphate 160g, pure water 350g, mixing is heated under agitation 100 DEG C, after constant temperature 2.5h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 420g of ionic liquid II, aqueous about 3.7wt%, yield 72wt%.
Dimethyl benzene ammonium chloride 600g, sodium hexafluoro phosphate 300g, pure water 550g, mixing is heated under agitation 70 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 550g of ionic liquid III, aqueous about 4.0wt%, yield 74wt%.
10g the and 2L distilled water of ionic liquid I is added in reactor, adjustment reaction temperature is 60 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 7.5, reaction 1h after, carry out it is aging, aging pH be 10, ageing time 30min, filter, 120 DEG C be dried 1h and obtain boehmite I.
15g the and 3L distilled water of ionic liquid I is added in reactor, adjustment reaction temperature is 70 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 8.0, reaction 1h after, carry out it is aging, aging pH be 10, ageing time 30min, filter, 120 DEG C be dried 1.5h and obtain boehmite II.
20g the and 3L distilled water of ionic liquid I is added in reactor, adjustment reaction temperature is 80 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 8.5, reaction 1h after, carry out it is aging, aging pH be 10, ageing time 30min, filter, 120 DEG C be dried 2h and obtain boehmite III.
Take 276g molybdenum oxides, 109g basic nickel carbonates are put into many mouthfuls of flasks, after adding a certain amount of deionized water, it is stirred until then vial matter be slowly added 72g phosphoric acid in pulpous state, it is slowly heated again after Deng initial action, kept for 90 DEG C～110 DEG C times of solution temperature be that 1h～3h. stops after heating, while hot filtering resulting solution, after filtering some insoluble impurity, the bottle green maceration extract I clarified is obtained, then to be added water and respectively obtain maceration extract II, III with certain proportion dilution maceration extract.The concentration of maceration extract I is MoO3：40g/100ml；NiO：9.5g/100ml；The concentration of maceration extract II is MoO3：54g/100ml；NiO：18g/100ml；The concentration of maceration extract III is MoO3：79g/100ml；NiO：28g/100ml.
The boehmite I of 150g is placed in disk forming machine and is sufficiently mixed, the inclination angle for adjusting rotating disk is 40o, and the rotating speed of rotating disk is 10rpm；Jing after blended contact on the boehmite I that sprayer is sprayed onto the mixed aqueous solution of the mixed aqueous solution of 10g ionic liquid I and 75g water and 30ml maceration extracts I and 75g water in rotating disk, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma I of 0.1～0.5mm of diameter；
Spheric catalyst presoma I prepared by the boehmite II and above-mentioned steps of 150g is sufficiently mixed in disk forming machine, the inclination angle for adjusting rotating disk is 50o, and the rotating speed of rotating disk is 15rpm；Jing after blended contact on the boehmite II that sprayer is sprayed onto the mixed aqueous solution of the mixed aqueous solution and 46ml maceration extracts II and 75g water of 15g ionic liquids II and 75g water in rotating disk, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma II of 1.0～1.5mm of diameter；
Spherical precursor II prepared by the boehmite III and above-mentioned steps of 150g is sufficiently mixed in disk forming machine, the inclination angle for adjusting rotating disk is 50o, and the rotating speed of rotating disk is 15rpm；Jing after blended contact on the boehmite III that sprayer is sprayed onto the mixed aqueous solution of the mixed aqueous solution and 69ml maceration extracts III and 75g water of 21g ionic liquids III and 75g water in rotating disk, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma III of 1.0～1.5mm of diameter；Spheric catalyst presoma III is dried into 2h through 150 DEG C, after 600 DEG C of roasting 2h, required spheric catalyst is obtained, CT-2 is denoted as, property is listed in Table 1 below.
Embodiment 3
Ammonio methacrylate 250g, ammonium tetrafluoroborate 150g, pure water 300g, mixing is heated under agitation 90 DEG C, after constant temperature 1.5h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains ionic liquid I 300g, aqueous about 3.5wt%, yield 73wt%.
Etamon chloride 450g, sodium hexafluoro phosphate 250g, pure water 500g, mixing is heated under agitation 90 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 650g of ionic liquid II, aqueous about 3.9wt%, yield 75wt%.
Aminomethyl phenyl ammonium chloride 500g, sodium hexafluoro phosphate 260g, pure water 450g, mixing is heated under agitation 90 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 550g of ionic liquid III, aqueous about 3.5wt%, yield 74wt%.
15g the and 2L distilled water of ionic liquid I is added in reactor, adjustment reaction temperature is 65 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 8.0, after reaction 1h, carries out aging, and aging pH is 9.0, ageing time 30min, filter, 110 DEG C be dried after 2.5h and obtain boehmite I.
20g the and 3L distilled water of ionic liquid I is added in reactor, adjustment reaction temperature is 75 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 8.0, after reaction 1.5h, carries out aging, and aging pH is 9.0, ageing time 30min, filter, 110 DEG C be dried after 2.0h and obtain boehmite II.
24g the and 3L distilled water of ionic liquid I is added in reactor, adjustment reaction temperature is 85 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）And aluminum sulfate（In terms of aluminum oxide, concentration is 8g/mL）Cocurrent is neutralized reaction, and pH value is 8.5, after reaction 1h, carries out aging, and aging pH is 9.0, ageing time 30min, filter, 110 DEG C be dried after 2.0h and obtain boehmite III.
Take 525g molybdenum oxides, 159g basic nickel carbonates are put into many mouthfuls of flasks, after adding a certain amount of deionized water, it is stirred until then vial matter be slowly added 125g phosphoric acid in pulpous state, it is slowly heated again after Deng initial action, kept for 90 DEG C～110 DEG C times of solution temperature be that 1h～3h. stops after heating, while hot filtering resulting solution, after filtering some insoluble impurity, the bottle green maceration extract I clarified is obtained, then to be added water and respectively obtain maceration extract II, III with certain proportion dilution maceration extract.The concentration of maceration extract I is MoO3：36g/100ml；NiO：8.4g/100ml；The concentration of maceration extract II is MoO3：50g/100ml；NiO：17g/100ml；The concentration of maceration extract III is MoO3：71g/100ml；NiO：26g/100ml.
The boehmite I of 200g is placed in disk forming machine and is sufficiently mixed, the inclination angle for adjusting rotating disk is 50o, and the rotating speed of rotating disk is 20rpm；Jing after blended contact on the boehmite I that sprayer is sprayed onto the mixed aqueous solution of the mixed aqueous solution of 15g ionic liquid I and 90g water and 42ml maceration extracts I and 90g water in rotating disk, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma I of 0.1～0.5mm of diameter；
Spheric catalyst presoma I prepared by the boehmite II and above-mentioned steps of 200g is sufficiently mixed in disk forming machine, the inclination angle for adjusting rotating disk is 50o, and the rotating speed of rotating disk is 20rpm；Jing after blended contact on the boehmite II that sprayer is sprayed onto the mixed aqueous solution of the mixed aqueous solution and 58ml ionic liquids II and 90g water of 20g ionic liquids II and 90g water in rotating disk, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma II of 1.0～1.5mm of diameter；
Spheric catalyst presoma II prepared by the boehmite III and above-mentioned steps of 200g is sufficiently mixed in disk forming machine, the inclination angle for adjusting rotating disk is 50o, and the rotating speed of rotating disk is 20rpm；Jing after sprayer is by blended contact on the boehmite III in the mixed aqueous solution to rotating disk of the mixed aqueous solution sprinkling of 36g ionic liquids III and 90g water and 90ml maceration extracts and 90g water, molding time of the material in rotating disk is 10min, obtains the spheric catalyst presoma III of 1.0～1.5mm of diameter；Spherical precursor III is dried into 4h through 120 DEG C, after 550 DEG C of roasting 2.5h, required spheric catalyst is obtained, CT-3 is denoted as, property is listed in Table 1 below.
Comparative example 1
2L distilled water is added in reactor, adjustment reaction temperature is 70 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）With aluminum sulfate in terms of aluminum oxide, concentration is neutralized reaction for 8g/mL cocurrents, and pH value is 7.5, after reaction 1h, carries out aging, and aging pH is 11, ageing time 30min, filters, is dried to obtain required boehmite.
The above-mentioned modified boehmite of 600g is placed in disk forming machine and is sufficiently mixed, the inclination angle for adjusting rotating disk is 40o, and the rotating speed of rotating disk is 15rpm；Jing sprayers are by 180g water and/or and binding agent（Containing 540g water, 28g nitric acid）Mixed solution and 180ml embodiments 3 in maceration extract III be sprayed onto on the modified boehmite in rotating disk after blended contact, molding time of the material in rotating disk be 30min, obtain the spherical precursor of 1.0～1.5mm of diameter；Spherical precursor is dried into 4h through 120 DEG C, after 600 DEG C of roasting 3h, required spheric catalyst is obtained, CD-1 is denoted as, property is listed in Table 1 below.
Comparative example 2
In aluminum sulfate aqueous solution（In terms of aluminum oxide, concentration is 8g/mL）Middle addition adds ammonium tetrafluoroborate and sodium hexafluoro phosphate by the consumption of embodiment 1, obtains the aluminum sulfate solution of fluorine-containing, boron and phosphorus.2L distilled water is added in reactor, adjustment reaction temperature is 70 DEG C, by sodium metaaluminate（In terms of aluminum oxide, concentration is 26g/mL）Be neutralized reaction with the aluminum sulfate solution cocurrent of fluorine-containing, boron and phosphorus, pH value is 7.5, reaction 1h after, carry out it is aging, aging pH be 11, ageing time 30min is filtered, is dried to obtain modified boehmite.
The above-mentioned modified boehmite of 450g is placed in disk forming machine and is sufficiently mixed, the inclination angle for adjusting rotating disk is 40o, and the rotating speed of rotating disk is 10rpm；Jing sprayers are by 360g water and/or and binding agent（Containing 360g water, 29g nitric acid）Mixed solution and 210ml embodiments 3 in maceration extract III be sprayed onto on the modified boehmite in rotating disk after blended contact, molding time of the material in rotating disk be 30min, obtain the spherical precursor of 1.0～1.5mm of diameter；Spherical precursor is dried into 4h through 120 DEG C, after 600 DEG C of roasting 3h, required spheric catalyst is obtained, CD-2 is denoted as, property is listed in Table 1 below.
Comparative example 3
Compared with Example 1, ionic liquid II, III is changed into ionic liquid I, consumption keeps constant, while changing maceration extract I, II into maceration extract III obtains spheric catalyst CD-3, property is listed in Table 1 below.
The property of the catalyst of table 1.
Table 1（It is continuous）
Active appraisal experiment：
Catalyst in embodiment 1-3 and comparative example 1-3 is carried out into the activity rating of catalyst with the miscella of VGO and DAO as raw material, catalyst activity evaluation experimental is carried out on 50mL small hydrogenation devices, and presulfurization is carried out to catalyst before activity rating.Catalyst is in reaction stagnation pressure 8.0MPa, volume space velocity 1.0h during liquid-1, hydrogen to oil volume ratio 800：1, reaction temperature is 380 DEG C, after 2000h operatings, the results are shown in Table 2 and 3.
The raw material oil nature of table 2.
The catalyst activity evaluation result of table 3.
From table 3, the hydrodenitrogeneration of catalyst prepared by the present invention, hydrodesulfurization and metal removal activity are significantly better than comparative example.
Claims (13)
1. a kind of spherical hydrogenation catalyst composition, including hydrogenation active metals, auxiliary agent and alumina support；Described hydrogenation active metals component is one or more in vib metals and group VIII metal, on the basis of the weight of catalyst, vib metals oxide content is 5.0wt% ~ 30.0wt%, and group VIII metal oxide content is 0.5wt% ~ 10.0 wt%；Auxiliary agent is the one kind in several combinations of following I, II and III：I- fluorine and phosphorus, II- fluorine and boron, III- fluorine, phosphorus and boron；Auxiliary agent is calculated as 1.5% ~ 2.0% with element；Balance of alumina support；Described hydrogenation active metals concentration gradually increases from catalyst granules center to outer surface, and the hydrogenation active metals concentration at the wherein 1/4R in catalyst granules, at 1/2R and at R meets following proportionate relationship：C1/4R：C1/2R：CR=1：1.5~2.0：2.5～3.0；Assistant concentration gradually increases from catalyst granules center to outer surface, at the wherein 1/4R in catalyst granules, the assistant concentration at 1/2R and at R meet following proportionate relationship：C1/4R：C1/2R：CR=1：2~4：3~5；Wherein R is the radius of the catalyst granules with spheric catalyst composition center as initial point.
2. according to the carbon monoxide-olefin polymeric described in claim 1, it is characterised in that：200 ~ the 250m of specific surface area of described spherical hydrogenation catalyst composition2/ g, 0.4 ~ 0.7ml/g of pore volume, with dual pore distribution, aperture is 10 ~ 15nm and 15 ~ 30nm；The wherein pore size distribution of 10 ~ 15nm accounts for total pore volume 35% ~ 40%, and the pore size distribution of 15-30nm accounts for the 30% ~ 35% of total pore volume.
3. according to the carbon monoxide-olefin polymeric described in claim 1 or 2, it is characterised in that：Described vib metals are W and/or Mo, and group VIII metal is Co and/or Ni.
4. according to the carbon monoxide-olefin polymeric described in claim 1 or 2, it is characterised in that：When auxiliary agent is I, fluorine accounts for the 50%～55% of auxiliary agent quality, and phosphorus accounts for the 45%～50% of auxiliary agent gross mass；When auxiliary agent is II, fluorine accounts for the 50%～55% of auxiliary agent quality, and boron accounts for the 45%～50% of auxiliary agent gross mass；When auxiliary agent is III, fluorine accounts for the 50%～55% of auxiliary agent total amount, and phosphorus accounts for the 30% ~ 35% of auxiliary agent total amount, and boron accounts for the 15%～20% of auxiliary agent total amount.
5. the preparation method of the spherical hydrogenation catalyst composition described in a kind of claim 1 or 2, it is characterised in that including following content：
（1）The preparation of ionic liquid
Ionic liquid I, II and III are made respectively with M2, M3, M4 by M1；
The M1 is one or more in ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate ammonium hexafluorophosphate, sodium hexafluoro phosphate, Potassium Hexafluorophosphate etc.；
Described M2 is that carbon number is one or more in the alkyl ammonium halide of 1 ~ 4；
Described M3 is that carbon number is one or more in the alkyl ammonium halide of 4 ~ 8, and alkyl is one or more in methyl, ethyl, propyl group；
Described M4 is that carbon number is one or more in the alkyl ammonium halide of 8 ~ 12；
（2）The preparation of boehmite
Ionic liquid I is added during sodium aluminate solution and aluminum sulfate solution plastic, after cemented into bundles, carries out aging, then filtered, after being dried boehmite I is obtained；
Ionic liquid II is separately added into during sodium aluminate solution and aluminum sulfate solution plastic, after cemented into bundles, carries out aging, then filtered, after being dried boehmite II is obtained；
Ionic liquid III is separately added into during sodium aluminate solution and aluminum sulfate solution plastic, after cemented into bundles, carries out aging, then filtered, after being dried boehmite III is obtained；
（3）The preparation of hydrogenation active metals solution
Prepare maceration extract I, II and III that hydrogenation active metals concentration gradually increases, in terms of oxide, the concentration of hydrogenation active metals is 36 ~ 50g/100ml in maceration extract I, the concentration of hydrogenation active metals is 60 ~ 75 g/100ml in maceration extract II, the concentration of hydrogenation active metals is 20 ~ 30 g/100ml for the concentration increasing degree of 85 ~ 110 g/100ml, wherein maceration extract I and II or maceration extract II and III in maceration extract III；
（4）The preparation of spherical hydrogenation catalyst composition
Boehmite I is placed in disk forming machine and is sufficiently mixed, and Jing sprayers are sprayed onto the ionic liquid I aqueous solution and maceration extract I on the aluminum oxide in rotating disk, after blended contact, obtains spheric catalyst presoma I；
Boehmite II is sufficiently mixed with spheric catalyst presoma I in disk forming machine again, the Jing atomizers sprays ionic liquid II aqueous solution and maceration extract II, after blended contact, spheric catalyst presoma II；
Then boehmite III is sufficiently mixed with spheric catalyst presoma II in disk forming machine, the Jing atomizers sprays ionic liquid III aqueous solution and maceration extract III, after blended contact, obtain spheric catalyst presoma III, drying, obtains spherical hydrogenation catalyst composition after roasting.
6. in accordance with the method for claim 5, it is characterised in that：Step（1）The preparation method of intermediate ion liquid I is to be added to the water M1 and M2, and reaction temperature is heated under agitation, and isothermal reaction after reaction terminates, is cooled down, and centrifugation obtains ionic liquid I；The mol ratio of wherein M1 and M2 is 1：1～1：2, reaction condition is generally reaction temperature for 60～150 DEG C, and the isothermal reaction time is 1～4h；The preparation method and preparation condition of ionic liquid II and III is identical with ionic liquid I, and the M2 in said method is substituted for into M3 or M4, that is, obtain ionic liquid II or ionic liquid III.
7. in accordance with the method for claim 5, it is characterised in that：Step（2）The sodium aluminate solution is with aluminum sulfate solution Gelation Conditions：Reaction temperature is 50 ~ 80 DEG C, and pH value is 6.5 ~ 9.0, and the reaction time is 0.5 ~ 2.0 hour；Aging condition is as follows after plastic：Aging temperature is 50 ~ 80 DEG C, and pH value is 8.5 ~ 11.0, and ageing time is 0.1 ~ 1.0 hour；, as 10 ~ 30g/100mL, the concentration that aluminum sulfate solution is counted with aluminum oxide is as 3 ~ 10g/100mL for the concentration that sodium aluminate solution used is counted with aluminum oxide.
8. in accordance with the method for claim 5, it is characterised in that：Step（2）The addition of ionic liquid I, II and III is calculated with the amount of its auxiliary element for containing, auxiliary element in wherein ionic liquid I accounts for catalyst combination amount of substance for 0.2wt～0.45wt%, it is 0.55wt～0.9wt% that auxiliary element in ionic liquid II accounts for catalyst combination amount of substance, and the auxiliary element in ionic liquid III accounts for catalyst combination amount of substance for 0.95wt～1.35wt%.
9. in accordance with the method for claim 5, it is characterised in that：Step（2）Described in baking temperature be 40～200 DEG C, drying time be 1～5 hour.
10. in accordance with the method for claim 5, it is characterised in that：Step（4）Described in maceration extract I, II and III the hydrogenation active metals amount that contained with it of addition calculating, hydrogenation active metals in wherein maceration extract I counted with oxide the quality for accounting for carbon monoxide-olefin polymeric as 8.5wt～10.0wt%, hydrogenation active metals in maceration extract II counted with oxide the quality for accounting for carbon monoxide-olefin polymeric as 15.0wt～18.0wt%, the hydrogenation active metals in maceration extract III counted with oxide the quality for accounting for carbon monoxide-olefin polymeric as 20wt～25wt%.
11. in accordance with the method for claim 5, it is characterised in that：Step（4）The concentration of the intermediate ion liquid I aqueous solution represents that its concentration is 8～15% with ionic liquid mass percent in aqueous；The concentration of the ionic liquid II aqueous solution is 15～20%；The concentration of the aqueous solution of ionic liquid III is 22 ~ 25%；The concentration difference of ionic liquid I and ionic liquid II is 3～5%；Ionic liquid II is 3～5% with the concentration difference of ionic liquid III.
12. in accordance with the method for claim 5, it is characterised in that：Step（4）Described in the auxiliary element amount that contained with it of ionic liquid I, II and III addition calculating, it is 0.2wt～0.45wt% that auxiliary element in wherein ionic liquid I accounts for the quality of carbon monoxide-olefin polymeric, it is 0.55wt～0.9wt% that auxiliary element in ionic liquid II accounts for the quality of carbon monoxide-olefin polymeric, and it is 0.95wt～1.35wt% that the auxiliary element in ionic liquid III accounts for the quality of carbon monoxide-olefin polymeric.
Spherical hydrogenation catalyst composition described in a kind of 13. claims 1 or 2 is applied to wax oil, residual hydrogenation reaction.
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