CN103301888B - Preparation method of catalyst carrier for hydrotreating pretreatment of wax oil - Google Patents
Preparation method of catalyst carrier for hydrotreating pretreatment of wax oil Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst carrier for hydrotreating pretreatment of wax oil. The carrier prepared by the method comprises the main components and contents based on the carrier by weight percent: 25 to 45wt% of a silicon aluminum-phosphorus aluminum composite molecular sieve, 30 to 60wt% of macroporous alumina, and 15 to 45% of modified alumina, wherein the silicon aluminum-phosphorus aluminum composite molecular sieve is a composite molecular sieve with silicon aluminum or modified aluminosilicate zeolites serving as a core and a phosphorus aluminum or modified phosphorus aluminum molecular sieve serving as a housing, and has the specific surface area of 250 to 400m<2>/g and pore volume of 0.50 to 0.80cm<3>/g. The carrier is characterized in that the silicon aluminum-phosphorus aluminum composite molecular sieve is introduced to improve the acidity of the carrier and adjust the distribution of hydroxide radicals on the aluminum oxide surface in order to disperse active metal components easily. The carrier is loaded with metallic oxides of VIB group and VIII group for preparing a catalyst, shows outstanding aromatic ring hydrogenation saturation capacity and cracking capacity respecting to C-S and C-N bonds in the hydrotreating process of the wax oil, and is applicable to the catalytic cracking and hydrocracking of raw materials.
Description
Technical field
The present invention relates to a kind of wax oil hydrogenation pretreatment catalyst carrier field, the preparation method of the wax oil hydrogenation pretreatment catalyst carrier particularly containing sial-phosphorus aluminium composite molecular screen.
Technical background
In the face of heaviness increasingly, the in poor quality of boundary's petroleum resources, the high quality increasingly of petroleum fuel products, to clean, the head that thus developing heavy crude Efficient Conversion and clear gusoline production technology becomes current petrochemical processing industry bends weight.Catalytic cracking and hydrocracking technology are by heavy oil lighting important technical.In catalytic cracking in recent years, hydrocracking raw material, straight-run gas oil ratio reduces gradually, and high-sulfur nitrogen wax oil, deep vacuum distillation wax oil, wax tailings and depitching wet goods component ratio inferior constantly increases, raw material is the trend of in poor quality increasingly, nitride in raw material has great negative effect to catalyst activity and product quality, thus forces Petrochemical Enterprises will carry out weighted BMO spaces to catalytic cracking, hydrocracking wax oil raw material.The performance of weighted BMO spaces directly affects the whole efficiency of catalytic cracking, hydrocracking process, becomes one of the key core technology of catalytic cracking, hydrocracking.
The exploitation focusing on catalyst of wax oil hydrogenation cracking preconditioning technique.Hydrogenation pretreatment catalyst is made up of carrier and active metal, and carrier is generally aluminium oxide, and active component is group vib and group VIII metal, metal oxide and metal sulfide.The acid weak core of alumina catalyst support is that exploitation high activity wax oil hydrogenation pretreatment catalyst is imperative.Hydrogenation pretreatment catalyst adopts aluminium oxide to be carrier usually, but due to the limitation of the aperture of aluminium oxide own and surface acidity, saturated the removing with heterocyclic nitrogen compound of the polycyclic aromatic hydrocarbon that the single catalyst prepared as carrier can not realize the degree of depth, needs the modification carrying out aluminium oxide.A new generation hydrogenation pretreatment catalyst exploitation aspect, needs to improve the pore structure of carrier, surface acidity and the interaction force between adjustment carrier and metal.
Chinese invention patent CN100469443C discloses a kind of hydrogenation catalyst, adopts SiO
2modified aluminas surface, increases Al
2o
3surface acidity, improve hydrogenation reaction performance.Chinese invention patent CN100556994C discloses a kind of hydrotreating catalyst, its carrier by titanium dioxide and silica composite oxide and HY molecular sieve or sour modified HY zeolite jointly as carrier, load active component, be prepared into catalyst, the introducing of Y molecular sieve, add the acidity of catalyst, improve hydrogenation reaction performance.Chinese invention patent (CN1769384A) discloses a kind of preparation method of heavy oil hydrogenating treatment catalyst, it is characterized in that a certain amount of Beta molecular sieve and aluminium oxide jointly as carrier, after impregnated activated component, be prepared into catalyst, but add acid strong molecular sieve modified carrier, though add the cracking activity of catalyst, but also increasing catalyst shows carbon deposition quantity, and the long period stability affecting hydrotreating catalyst is run.Chinese invention patent CN1015915610A discloses a kind of diesel oil hydrofining catalyst containing one-dimensional channels molecular sieve, on the basis of cracking preventing diesel oil distillate, realizes hydrotreated lube base oil and deep removal sulphur, the nitrogen compound of aromatic hydrocarbons.Chinese invention patent CN102019201A discloses a kind of preparation method of the heavy distillate Hydrobon catalyst containing molecular sieve, it is characterized in that with aluminium oxide, phosphate aluminium molecular sieve AlPO
4-5 and titanium silicon molecular sieve ETS-4-10 common as carrier, by the synergy of two kinds of molecular sieves, improve the hydrofinishing performance of catalyst, make it process bad heavy distillate comparatively relaxing under process conditions, reach deep desulfuration, denitrification effect.
Described in summary, wax oil hydrogenation pretreatment catalyst mainly carries out saturated many epithios, the organonitrogen removal of polycyclic aromatic hydrocarbon, the hydrotreated lube base oil of polycyclic aromatic hydrocarbon is mainly at hydrogenation sites, the fracture of C-S, C-N key mainly occurs in acid centre, therefore requires that hydrogenation pretreatment catalyst needs Proper Match hydrogenation sites and acid centre.Introduce the acid centre that molecular sieve can increase catalyst in hydrotreating catalyst disclosed in above technological invention patent, coordinate to carry out the saturated of polycyclic aromatic hydrocarbon and sulphur, the removing of nitrogen compound with hydrogenation sites.But single introducing molecular sieve effectively can not mate acid site and hydrogenation center, need comprehensively modifying carrier surface and the impregnated activated metal of latched position, high-activity hydrocracking pretreatment catalyst could be developed.
Summary of the invention
For the weak point of above technology, the invention provides a kind of preparation method of wax oil hydrogenation pretreatment catalyst carrier, the method introduces the acidity that sial-phosphorus aluminium composite molecular screen not only can increase carrier, alumina surface hydroxyl can also be regulated to distribute, be conducive to the dispersion of active metal.The density in II class activated centre is added with hydrogenation pretreatment catalyst prepared by carrier of the present invention, the introducing of composite molecular screen, for catalyst provides B acid site, more reasonably mate hydrogenation sites and the acid site of catalyst, improve the hydrotreated lube base oil performance of polycyclic aromatic hydrocarbon and the lytic activity of C-S, C-N key.
In order to reach above technical purpose, the invention provides a kind of preparation method of wax oil hydrogenation pretreatment catalyst carrier, it is characterized in that, by the mass percent of carrier, the component of described carrier and content are: sial-phosphorus aluminium composite molecular screen 25 ~ 45wt%, macroporous aluminium oxide 30 ~ 60wt% and modified aluminas 15 ~ 45wt%, wherein said sial-phosphorus aluminium composite molecular screen is that phosphorus aluminium or modification phosphate aluminium molecular sieve are the composite molecular screen of shell with sial or modification Si-Al zeolite for core; Described modified aluminas is to alumina modified gained by one or more elements in silicon, titanium, zirconium; Described carrier specific area is 250 ~ 400 m
2/ g, pore volume is 0.50 ~ 0.80 cm
3/ g;
The preparation method of described wax oil hydrogenation process catalyst carrier comprises the following steps:
1) synthesis of sial-phosphorus aluminium composite molecular screen: by phosphoric acid, boehmite mixes with deionized water, add silicon source or modified metal soluble-salt as required, then poly-N is added, N-bis-tetraethyl ammonium hydrochloride, finally add template, stir and form homogeneous gel mixture system, described gel mixture is loaded in autoclave, after at 60 ~ 100 DEG C of temperature, crystallization 2 ~ 8 H-shaped becomes phosphate aluminium molecular sieve crystal seed, add sial or modification Si-Al zeolite, water-heat transfer crystallization 12 ~ 48 h at 160 ~ 200 DEG C of temperature, by crystallization products therefrom through being separated, naturally dry, dry, sial-phosphorus aluminium composite molecular screen is obtained after roasting,
2) extrusion aid is added in the former powder of mixing mixed with macroporous aluminium oxide, modified aluminas by sial-phosphorus aluminium composite molecular screen that step 1) is synthesized, then add expanding agent solubility solution and acidic mixed solution and carry out kneading, extruded, finally by the carrier naturally dried, dry, roasting obtains hydrogenation pretreatment catalyst;
Wherein, boehmite in described gel mixture system, phosphoric acid, template, modified metal soluble-salt, N, the mol ratio of N-bis-tetraethyl ammonium hydrochloride and water is 1:(0.5 ~ 2.0): (0.5 ~ 2.5): (0.1 ~ 0.5): (0.01 ~ 0.2): (20 ~ 100), wherein boehmite, phosphoric acid, modified metal soluble-salt are respectively with Al
2o
3, P
2o
5with modified metal-oxide meter.
In technique scheme, described phosphate aluminium molecular sieve is preferably the AlPO of AFI type
4-5, the AlPO of AEL type
4-11, the AlPO of ATO type
4-31 and the AlPO of AFO type
4-41, or by the element modified phosphate aluminium molecular sieve of Si, Mg, Zn, Co, Mn, Fe; Described Si-Al zeolite is preferably one or more in ZSM-5, Y, Beta, ZSM-22, ZSM-23 and modified ZSM-5, Y, Beta, ZSM-22, ZSM-23;
In step 1), synthesizing described AFI type phosphate aluminium molecular sieve template is triethylamine; Synthesize described AEL, ATO and AFO type phosphate aluminium molecular sieve template is di-n-propylamine or diisopropylamine; Described silicon source is one or several in ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, acidic silicasol, white carbon and active silica, and described Mg, Zn, Co, Mn and Fe modified metal salt is preferably one or more in soluble nitrate, sulfate, chlorate and acetate; The baking temperature of described crystallization product is 120 ~ 180 DEG C, after dry 4 ~ 24 h, and obtained sial-phosphorus aluminium composite molecular screen after 520 ~ 600 DEG C of roasting 2 ~ 12 h;
Step 2) in, described extrusion aid is that sesbania powder is or/and methylcellulose, described expanding agent is soluble starch or polyethylene glycol, described acid solution is nitric acid, citric acid and tartaric mixed solution, the each constituent mass percentage composition of the former powder of wherein said mixing is counted with contents on dry basis: sial-phosphorus aluminium composite molecular screen 25 ~ 45wt%, macroporous aluminium oxide 30 ~ 60wt% and modified aluminas 15 ~ 45wt%, described extrusion aid, expanding agent, nitric acid, citric acid, tartaric addition is followed successively by the 3wt% ~ 6wt% mixing former powder, 2wt% ~ 8wt%, 3 ~ 6wt%, 1 ~ 3wt% and 1 ~ 3wt%, the addition of water is 0.5:1 ~ 1.0:1 with mixing former powder mass ratio, described baking temperature is 100 ~ 150 DEG C, and drying time is 6 ~ 36 h, and after dry, DEG C roasting 2 ~ 12 h in temperature programming to 450 ~ 600 obtains catalyst carrier.
In technique scheme, described sial-phosphorus aluminium composite molecular screen specific area is 200 ~ 500 m
2/ g, pore volume is 0.30 ~ 0.60 cm
3/ g, acid amount 0.20 ~ 0.80 mmol/g; Wherein the mass ratio of phosphate aluminium molecular sieve and Si-Al zeolite is 1:0.1 ~ 1:10.0.
In technique scheme, the specific area of described modified aluminas is 300 ~ 450 m
2/ g, pore volume is 0.60 ~ 0.90 cm
3/ g; Wherein total addition of modifying element oxide accounts for the quality of modified aluminas is 5 ~ 25%.
In technique scheme, it is spherical that the profile of described wax oil hydrogenation pretreatment catalyst carrier is preferably clover, bunge bedstraw herb, butterfly or tooth, most wherein preferably is butterfly or tooth is spherical.
Compared with prior art, its beneficial effect is as follows in the present invention:
Carrier of hydrogenating catalyst of the present invention is using sial-phosphorus aluminium composite molecular screen, macroporous aluminium oxide and modified aluminas as raw material.Wherein component sial-phosphorus aluminium composite molecular screen is for core with Si-Al zeolite or modification Si-Al zeolite, with phosphate aluminium molecular sieve or modification phosphorus aluminium zeolite, the phosphoric acid introduced in its sieve synthesis procedure is not only as the phosphoric acid of phosphate aluminium molecular sieve synthesis, phosphoric acid also carries out modification to Si-Al zeolite simultaneously, and the acid amount of modulation zeolite distributes with acid.The introducing of sial-phosphorus aluminium composite molecular screen not only can increase the acidity of carrier, alumina surface hydroxyl can also be regulated to distribute, be conducive to the dispersion of active metal." AlPO4 " structure of crystal, is conducive to the formation suppressing passive nickel aluminate, regulates the interaction force between metal and carrier.Carrier of the present invention adds the density in II class activated centre when hydrogenation pretreatment catalyst prepared by supported active metals, the introducing of composite molecular screen, for catalyst provides B acid site, more reasonably mate hydrogenation sites and the acid site of catalyst, improve the hydrotreated lube base oil performance of catalyst to polycyclic aromatic hydrocarbon and the cracking ability of C-S, C-N key.After the carrier loaded active metal of wax oil hydrogenation pretreatment catalyst of the present invention is prepared into catalyst, can be applicable to the weighted BMO spaces of faulty wax oil, be adapted to the weighted BMO spaces of catalytic cracking, hydrocracking raw material especially.
Detailed description of the invention
Describe technical characterstic of the present invention with specific embodiment below, but be not limited only to this.
Embodiment-1
HY/AlPO
4the synthesis of-5 composite molecular screens: by 109.0 g phosphoric acid (AR, mass concentration 85%) mix in 35 DEG C of water-baths with 306.0 g deionized waters, add 60.0 g boehmites (Shandong aluminium powder, alundum (Al2O3) content 67.0wt%), constant temperature uniform stirring 0.5 h, obtains aluminium phosphate sol; Add 4.0 g and gather N, N-bis-tetraethyl ammonium hydrochloride (is called for short PCD, the pure Co., Ltd of henna academic libraries, purity 95%), after slowly stirring 0.5 h, add 64.0 g triethylamines and (be called for short TEA, purity 99%), continue stirring 0.5 h to forming even colloidal sol, the molar ratio of material in this reaction system is Al
2o
3: P
2o
5: TEA:H
2o=1:1.05:1.2:50.Colloidal sol is loaded in polytetrafluoroethylene (PTFE) autoclave, under 100 DEG C (heating rate 1 DEG C/min) after aging 4 h, obtain AlPO
4-5 molecular sieve crystal seeds, then add 45.0 g HY molecular sieves (Shanghai Xin Nian auxiliary agent Co., Ltd, silica alumina ratio is 2.5), at 185 DEG C after crystallization 24 h.Be separated by product after crystallization, the washing of gained solid matter with deionized water is to pH=7 ~ 8, and at 120 DEG C, dry process 12 h, obtain HY/AlPO
4the former powder of-5 composite molecular screen; By former powder after 580 DEG C of (heating rate 2 DEG C/min) roasting 4 h, obtain HY/AlPO
4-5 composite molecular screens.
Embodiment-2
The synthesis of USY/SAPO-5 composite molecular screen: mixed in 35 DEG C of water-baths with 306.0 g deionized waters by 109.0 g phosphoric acid, adds 60.0 g boehmites, and constant temperature uniform stirring 0.5 h, obtains aluminium phosphate sol; Add 4.0 g PCD, after slowly stirring 0.5 h, add 16.0 g ethyl orthosilicates and (be called for short TEOS, purity 99%), after then slowly stirring 0.5 h, add 64.0 g TEA, continue stirring 0.5 h to forming even colloidal sol, the molar ratio of material in this reaction system is Al
2o
3: P
2o
5: SiO
2: TEA:H
2o=1:1.05:0.2:1.2:50.Colloidal sol is loaded in polytetrafluoroethylene (PTFE) autoclave, under 90 DEG C (heating rate 1 DEG C/min) after aging 8 h, obtain SAPO-5 molecular sieve crystal seed, then add 40.0 g USY(Shanghai Xin Nian auxiliary agent Co., Ltds, silica alumina ratio is 12) molecular sieve, at 185 DEG C after crystallization 24 h.Be separated by product after crystallization, the washing of gained solid matter with deionized water is to pH=7 ~ 8, and at 120 DEG C, dry process 8 h, obtain the former powder of USY/SAPO-5 composite molecular screen; By former powder after 580 DEG C of (heating rate 2 DEG C/min) roasting 4 h, obtain USY/SAPO-5 composite molecular screen.
Embodiment-3
Beta/AlPO
4the synthesis of-5 composite molecular screens: mixed in 35 DEG C of water-baths with 306.0 g deionized waters by 114.0 g phosphoric acid, adds 60.0 g boehmites, and constant temperature uniform stirring 0.5 h, obtains aluminium phosphate sol; Add 4.0 g PCD, after stirring slow 0.5 h, add 64.0 g TEA, continue stirring 0.5 h to forming even colloidal sol, the molar ratio of material in this reaction system is Al
2o
3: P
2o
5: TEA:H
2o=1:1.1:1.2:50.Colloidal sol is loaded in polytetrafluoroethylene (PTFE) autoclave, under 100 DEG C (heating rate 1 DEG C/min) after aging 4 h, obtain AlPO
4-5 molecular sieve crystal seeds, then add 45.0 g Beta molecular sieves (Shanghai Xin Nian auxiliary agent Co., Ltd, silica alumina ratio is 24), at 175 DEG C after crystallization 36 h.Be separated by product after crystallization, the washing of gained solid matter with deionized water is to pH=7 ~ 8, and at 120 DEG C, dry process 8 h, obtain Beta/AlPO
4the former powder of-5 composite molecular screen; By former powder after 550 DEG C of (heating rate 2 DEG C/min) roasting 6 h, obtain Beta/AlPO
4-5 composite molecular screens.
Embodiment-4
The synthesis of USY/SAPO-11 composite molecular screen: mixed in 38 DEG C of water-baths with 320.0 g deionized waters by 120.0 g phosphoric acid, adds 65.0 g boehmites, and in 38 DEG C of water-baths, magnetic agitation 0.5 h, obtains aluminium phosphate sol; Add 6.0 g PCD, after slowly stirring 0.5 h, add 16.0 g TEOS, after continuing stirring 0.5 h, add 72.0 di-n-propylamines (being called for short TEA, purity 98%), continue stirring 0.5 h to forming even colloidal sol (mixed solution), the molar ratio of material in this reaction system is Al
2o
3: P
2o
5: SiO
2: TEA:H
2o=1:1.1:0.3:1.2:55.Colloidal sol is loaded in polytetrafluoroethylene (PTFE) autoclave, under 100 DEG C (heating rate 1 DEG C/min) after aging 4 h, obtain SAPO-11 crystal seed, then add 50.0 g USY molecular sieve, at 180 DEG C after crystallization 24 h.Be separated by product after crystallization, the washing of gained solid matter with deionized water is to pH=7 ~ 8, and at 120 DEG C, dry process 12 h, obtain the former powder of USY/SAPO-11 composite molecular screen; By former powder after 600 DEG C of (heating rate 2 DEG C/min) roasting 4 h, obtain USY/SAPO-11 composite molecular screen.
Embodiment-5
The synthesis of Beta/CoAPO-5 composite molecular screen: mixed in 38 DEG C of water-baths with 306.0 g deionized waters by 109.0 g phosphoric acid (AR, 85%), add 60.0 g boehmites, constant temperature uniform stirring 0.5 h, obtains aluminium phosphate sol; Add 6.0 g PCD, after slowly stirring 0.5 h, add 24.0 g cobalt acetates, after slow stirring 0.5 h, add 64.0 g triethylamines and (be called for short TEA, AR, 99%), continue stirring 0.5 h to forming even colloidal sol (mixed solution), the molar ratio of material in this reaction system is Al
2o
3: P
2o
5: Co
2o
3: TEA:H2O=1:1.05:0.1:1.2:50.Colloidal sol is loaded in polytetrafluoroethylene (PTFE) autoclave, under 90 DEG C (heating rate 1 DEG C/min) after aging 4 h, obtains CoAPO-5 crystal seed, then add 40.0 g Beta(silica alumina ratios 24) molecular sieve, at 190 DEG C after crystallization 36 h.Product after crystallization is carried out centrifugation, and the washing of gained solid matter with deionized water is to pH=7 ~ 8, and at 120 DEG C, dry process 12 h, obtain the former powder of Beta/CoAPO-5 composite molecular screen; By former powder after 580 DEG C of (heating rate 2 DEG C/min) roasting 4 h, obtain Beta/CoAPO-5 composite molecular screen.
Embodiment-6
By 200.0 g macroporous aluminium oxides (Shandong Aluminum Co., Ltd. Co., Ltd, contents on dry basis 75%), 80.0 g AlPO
4-5/HY composite molecular screen (contents on dry basis 95%), 104.0 g Si modification aluminium oxide (Zibo Jin Qi Chemical Industry Science Co., Ltd, contents on dry basis 72%), 9.0 g sesbania powder and 9.0 g methylcellulose, drop into kneading machine mixed grind 15 min after mixing, be mixed with the former powder of mixing.By 120 g by deionized water (92wt%) and soluble starch (8wt%, Langfang Peng Cai Fine Chemical Co., Ltd, purity 99.8%) the expanding agent solution and 200.0 g that prepare disposable the pouring into of acid solution of being prepared by water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) mix in former powder, first kneading is to squeezing paste, be that 8 mm column type orifice plates respectively extrude once through hollow plate, diameter again, be finally extruded into the butterfly bar that diameter is 1.8 mm; The bar that wet by gained dries naturally, then in 120 DEG C of baking ovens dry 6 h, be finally placed on Muffle furnace Program and be warming up to 550 DEG C of roasting 4 h, namely obtain carrier S ZT-1.
Embodiment-7
By 200.0 g macroporous aluminium oxides, 80.0 g SAPO-5/USY composite molecular screens (contents on dry basis 95%), 100.0 g silicon, modified zirconia aluminium oxide (Zibo Jin Qi Chemical Industry Science Co., Ltd, contents on dry basis 75%), 9.0 g sesbania powder and 9.0 g methylcellulose, drop into kneading machine mixed grind 15 min after mixing, be mixed with the former powder of mixing.Disposable the pouring into of acid solution that the expanding agent solution prepared by deionized water (92wt%) and soluble starch (8wt%) by 100 g and 200.0 g are prepared by water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) mixes in former powder, first kneading is to squeezing paste, be that 8 mm column type orifice plates respectively extrude once through hollow plate, diameter again, be finally extruded into the butterfly shape bar that diameter is 1.8 mm; The bar that wet by gained dries naturally, then in 120 DEG C of baking ovens dry 6 h, be finally placed on Muffle furnace Program and be warming up to 550 DEG C of roasting 4 h, namely obtain carrier S ZT-2.
Embodiment-8
By 180.0 g macroporous aluminium oxides, 95.0 g AlPO
4-5/Beta composite molecular screen (contents on dry basis 96%), 104.0 g titanium modified aluminas (Zibo Jin Qi Chemical Industry Science Co., Ltd, contents on dry basis 72%), 9.0 g sesbania powder and 9.0 g methylcellulose, drop into kneading machine mixed grind 15 min after mixing, be mixed with the former powder of mixing.By 120 g by deionized water (92wt%) and polyethylene glycol (8wt%, Tianjin chemical reagent supply and marketing company, purity 99.0%) the expanding agent solution and 200.0 g that prepare disposable the pouring into of acid solution of being prepared by water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) mix in former powder, first kneading is to squeezing paste, be that 8 mm column type orifice plates respectively extrude once through hollow plate, diameter again, be finally extruded into the butterfly bar that diameter is 1.8 mm; The bar that wet by gained dries naturally, then in 120 DEG C of baking ovens dry 6 h, be finally placed on Muffle furnace Program and be warming up to 550 DEG C of roasting 4 h, namely obtain carrier S ZT-3.
Embodiment-9
By 180.0 g macroporous aluminium oxides, 80.0 g AlPO
4-5/Beta composite molecular screen (contents on dry basis 93%), 125.0 g Si modification aluminium oxide, 12.0 g sesbania powder and 6.0 g methylcellulose, drop into kneading machine mixed grind 15 min after mixing, be mixed with the former powder of mixing.Disposable the pouring into of acid solution that the expanding agent solution prepared by deionized water (90wt%) and polyethylene glycol (10wt%) by 120 g and 200.0 g are prepared by water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) mixes in former powder, first kneading is to squeezing paste, be that 8 mm column type orifice plates respectively extrude once through hollow plate, diameter again, be finally extruded into the butterfly bar that diameter is 1.8 mm; The bar that wet by gained dries naturally, then in 120 DEG C of baking ovens dry 6 h, be finally placed on Muffle furnace Program and be warming up to 550 DEG C of roasting 4 h, namely obtain carrier S ZT-4.
Embodiment-10
By 200.0 g macroporous aluminium oxides, 95.0 g SAPO-11/USY composite molecular screens (contents on dry basis 94%), 80.0 g Si modification aluminium oxide, 12.0 g sesbania powder and 6.0 g methylcellulose, drop into kneading machine mixed grind 15 min after mixing, be mixed with the former powder of mixing.Disposable the pouring into of acid solution that the expanding agent solution prepared by deionized water (90wt%) and soluble starch (10wt%) by 120 g and 200.0 g are prepared by water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) mixes in former powder, first kneading is to squeezing paste, be that 8 mm column type orifice plates respectively extrude once through hollow plate, diameter again, be finally extruded into the butterfly bar that diameter is 1.8 mm; The bar that wet by gained dries naturally, then in 120 DEG C of baking ovens dry 6 h, be finally placed on Muffle furnace Program and be warming up to 550 DEG C of roasting 4 h, namely obtain carrier S ZT-5.
Embodiment-11
By 180.0 g macroporous aluminium oxides, 90.0 g CoAPO-5/USY composite molecular screens (contents on dry basis 96%), 104.0 g silicon, modified zirconia aluminium oxide, 9.0 g sesbania powder and 9.0 g methylcellulose, drop into kneading machine mixed grind 15 min after mixing, be mixed with the former powder of mixing.Disposable the pouring into of acid solution that the expanding agent solution prepared by deionized water (90wt%) and polyethylene glycol (10wt%) by 120 g and 200.0 g are prepared by water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) mixes in former powder, first kneading is to squeezing paste, be that 8 mm column type orifice plates respectively extrude once through hollow plate, diameter again, be finally extruded into the butterfly bar that diameter is 1.8 mm; The bar that wet by gained dries naturally, then in 120 DEG C of baking ovens dry 6 h, be finally placed on Muffle furnace Program and be warming up to 550 DEG C of roasting 4 h, namely obtain carrier S ZT-6.
Comparative example-1
By 250.0 g macroporous aluminium oxides, 6.0 g sesbania powder and 3.0 g methylcellulose, after mixing, drop into kneading machine mixed grind 15 min, be mixed with the former powder of mixing.The acid solution that 240.0 g are prepared by water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) is disposable to be poured in the former powder of mixing, first kneading is to squeezing paste, be that 8 mm column type orifice plates respectively extrude once through hollow plate, diameter again, be finally extruded into the butterfly bar that diameter is 1.8 mm; The bar that wet by gained dries naturally, then in 120 DEG C of baking ovens dry 6 h, be finally placed on Muffle furnace Program and be warming up to 550 DEG C of roasting 4 h, namely obtain carrier DSZT-1.
Embodiment-12
The preparation of Ni-Mo maceration extract: get 180.0 g molybdenum trioxides (Jiangsu Jiangyan City Bond metal product plant, purity 99.8%), 60.0 g basic nickel carbonates (Xin Guang fine chemistry industry Co., Ltd of Fushun City, purity 99.8%) and 9.0 g citric acids put into there-necked flask, add 120 mL deionized waters, add thermal agitation, slowly instill 22.5 g phosphoric acid (mass concentration 85%), 100 DEG C are stirred 2 h, add deionized water the volume of maceration extract is settled to 300 mL after dissolving completely, make the concentration of each oxide in final maceration extract be: MoO
360g/100 mL, NiO 12g/100 mL, P
2o
54g/100 mL, the pH value of maceration extract is 1.6.
Getting each 65.0 g of exemplary carrier SZT-2, SZT-3, SZT-5 comparison example DHZT-1 carrier places in dipping tank, pour the above-mentioned maceration extract of certain volume into, after flooding 2 h, carrier after dipping is dried naturally, dry 8 h in 120 DEG C of baking ovens, finally be placed on Muffle furnace Program and be warming up to 480 DEG C of roasting 4 h, namely obtain wax oil hydrogenation pretreatment catalyst SHC-2, SHC-3, SHC-5, DHC-1.
The physico-chemical property of hydrogenation pretreatment catalyst carrier prepared by table-1 embodiment and comparison example
The physico-chemical property of hydrogenation pretreatment catalyst prepared by table-2 embodiments and comparison example
As can be seen from the table, introduce the total acid content that composite molecular screen and modified aluminas can improve catalyst in carrier, particularly enhance the B acid site of catalyst, be conducive to the fracture of catalyst to the hydrotreated lube base oil of polycyclic aromatic hydrocarbon and C-S, C-N key.
Embodiment-13
The activity rating of the pretreating catalyst by hydrocracking that the present embodiment introduction is prepared by the present invention and comparative catalyst.Evaluate on 200 mL fixed bed hydrogenation reaction units, its reaction condition is: reaction temperature is 380 DEG C, reaction pressure 10.0 MPa, hydrogen to oil volume ratio 800:1, volume space velocity 1.5 h
-1, its evaluation result as shown in Table-3.
The weighted BMO spaces performance of the catalyst that table-3 is prepared based on carrier of the present invention and comparative catalyst
* relative denitrification activity=ln (S
tol/ S
c)/ln (S
tol/ S
dC) * 100, wherein S
tolfor the total sulfur in feedstock oil, S
dCfor the sulfur content in comparative catalyst's hydrogenation products, S
cfor the sulfur content in other catalyst hydrogenation products;
* relative denitrification activity=ln (N
tol/ N
c)/ln (N
tol/ N
dC) * 100, wherein N
tolfor the total nitrogen in feedstock oil, N
dCfor the nitrogen content in comparative catalyst's hydrogenation products, N
cfor the nitrogen content in other catalyst hydrogenation products.
After the carrier loaded active metal of hydrogenation pretreatment catalyst prepared by the inventive method is prepared into catalyst, can be applicable to the weighted BMO spaces of faulty wax oil, be adapted to the weighted BMO spaces of catalytic cracking, hydrocracking raw material especially, the process regulation of usual hydrotreatment, weighted BMO spaces is: reaction temperature is 360 ~ 400 DEG C, reaction pressure 8.0 ~ 12.0 MPa, hydrogen to oil volume ratio 600:1 ~ 1000:1, volume space velocity 1.0 ~ 2.0h
-1.
Claims (6)
1. the preparation method of a wax oil hydrogenation pretreatment catalyst carrier, it is characterized in that, by the mass percent of carrier, the component of described carrier and content are: sial-phosphorus aluminium composite molecular screen 25 ~ 45wt%, macroporous aluminium oxide 30 ~ 60wt% and modified aluminas 15 ~ 45wt%, wherein said sial-phosphorus aluminium composite molecular screen is that phosphorus aluminium or modification phosphate aluminium molecular sieve are the composite molecular screen of shell with sial or modification Si-Al zeolite for core; Described modified aluminas is to alumina modified gained by one or more elements in silicon, titanium, zirconium; Described carrier specific area is 250 ~ 400m
2/ g, pore volume is 0.50 ~ 0.80cm
3/ g;
The preparation method of described wax oil hydrogenation process catalyst carrier comprises the following steps:
1) synthesis of sial-phosphorus aluminium composite molecular screen: by phosphoric acid, boehmite mixes with deionized water, add silicon source or modified metal soluble-salt as required, then poly-N is added, N-bis-tetraethyl ammonium hydrochloride, finally add template, stir and form homogeneous gel mixture system, described gel mixture is loaded in autoclave, after at 60 ~ 100 DEG C of temperature, crystallization 2 ~ 8h forms phosphate aluminium molecular sieve crystal seed, add sial or modification Si-Al zeolite, water-heat transfer crystallization 12 ~ 48h at 160 ~ 200 DEG C of temperature, by crystallization products therefrom through being separated, naturally dry, dry, sial-phosphorus aluminium composite molecular screen is obtained after roasting,
2) by step 1) add extrusion aid in the former powder of mixing that mixes with macroporous aluminium oxide, modified aluminas of sial-phosphorus aluminium composite molecular screen of synthesizing, then add expanding agent solubility solution and acidic mixed solution and carry out kneading, extruded, finally by the carrier naturally dried, dry, roasting obtains hydrogenation pretreatment catalyst;
Wherein, boehmite in described gel mixture system, phosphoric acid, template, modified metal soluble-salt, N, the mol ratio of N-bis-tetraethyl ammonium hydrochloride and water is 1:0.5 ~ 2.0:0.5 ~ 2.5:0.1 ~ 0.5:0.01 ~ 0.2:20 ~ 100, and wherein boehmite, phosphoric acid, modified metal soluble-salt are respectively with Al
2o
3, P
2o
5with modified metal-oxide meter.
2. method according to claim 1, is characterized in that, described phosphate aluminium molecular sieve comprises the AlPO of AFI type
4-5, the AlPO of AEL type
4-11, the AlPO of ATO type
4-31 and the AlPO of AFO type
4-41, or by the element modified phosphate aluminium molecular sieve of Si, Mg, Zn, Co, Mn, Fe; Described Si-Al zeolite is one or more in ZSM-5, Y, Beta, ZSM-22, ZSM-23 and modified ZSM-5, Y, Beta, ZSM-22, ZSM-23;
In step 1) in, synthesizing above-mentioned AFI type phosphate aluminium molecular sieve template is triethylamine; Synthesize above-mentioned AEL, ATO and AFO type phosphate aluminium molecular sieve template is di-n-propylamine or diisopropylamine; Described silicon source is one or several in ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, acidic silicasol, white carbon and active silica, and described modified metal salt comprises one or more in the soluble nitrate of Mg, Zn, Co, Mn and Fe, sulfate, chlorate and acetate; The baking temperature of above-mentioned crystallization product is 120 ~ 180 DEG C, after dry 4 ~ 24h, and obtained sial-phosphorus aluminium composite molecular screen after 520 ~ 600 DEG C of roasting 2 ~ 12h;
Step 2) in, described extrusion aid is that sesbania powder is or/and methylcellulose, described expanding agent is soluble starch or polyethylene glycol, described acid solution is nitric acid, citric acid and tartaric mixed solution, the each constituent mass percentage composition of the former powder of wherein said mixing is counted with contents on dry basis: sial-phosphorus aluminium composite molecular screen 25 ~ 45wt%, macroporous aluminium oxide 30 ~ 60wt% and modified aluminas 15 ~ 45wt%, described extrusion aid, expanding agent, nitric acid, citric acid, tartaric addition is followed successively by the 3wt% ~ 6wt% mixing former powder, 2wt% ~ 8wt%, 3 ~ 6wt%, 1 ~ 3wt% and 1 ~ 3wt%, the addition of water is 0.5:1 ~ 1.0:1 with mixing former powder mass ratio, described baking temperature is 100 ~ 150 DEG C, and drying time is 6 ~ 36h, and after dry, temperature programming to a 450 ~ 600 DEG C roasting 2 ~ 12h obtains catalyst carrier.
3. method according to claim 1, is characterized in that, described sial-phosphorus aluminium composite molecular screen specific area is 200 ~ 500m
2/ g, pore volume is 0.30 ~ 0.60cm
3/ g, acid amount 0.20 ~ 0.80mmol/g; Wherein the mass ratio of phosphate aluminium molecular sieve and Si-Al zeolite is 1:0.1 ~ 1:10.0.
4. method according to claim 1, is characterized in that, the specific area of described modified aluminas is 300 ~ 450m
2/ g, pore volume is 0.60 ~ 0.90cm
3/ g; Wherein total addition of modifying element oxide accounts for the quality of modified aluminas is 5 ~ 25%.
5. method according to claim 1, is characterized in that, the profile of described wax oil hydrogenation pretreatment catalyst carrier is that clover, bunge bedstraw herb, butterfly or tooth are spherical.
6. method according to claim 1, it is characterized in that, described wax oil hydrogenation pretreatment catalyst carrier is applied on faulty wax oil hydrogenation pretreatment catalyst, Controlling Technology condition is: reaction temperature is 360 ~ 400 DEG C, reaction pressure 8.0 ~ 12.0MPa, hydrogen to oil volume ratio 600:1 ~ 1000:1, volume space velocity 1.0 ~ 2.0h
-1.
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| CN106031885B (en) * | 2015-03-11 | 2018-07-24 | 中国石油天然气股份有限公司 | AlPO4-5/γ-Al2O3Composite material and preparation method and application |
| CN108722473B (en) * | 2018-06-04 | 2020-10-02 | 中国中化股份有限公司 | Preparation method of hydrocracking catalyst |
| CN109896532A (en) * | 2019-03-08 | 2019-06-18 | 宁夏大学 | A kind of method of modulation molecular sieve molded intensity and acidity |
| CN112717964B (en) * | 2019-10-28 | 2023-07-04 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method and application thereof |
| CN112791741B (en) * | 2019-11-14 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of hydrocracking catalyst |
| CN111701623B (en) * | 2020-06-23 | 2023-03-24 | 南开大学 | Hydrocracking isomerization catalyst, preparation method and application thereof |
| CN114452966B (en) * | 2020-10-22 | 2024-01-09 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina |
| CN114425361B (en) * | 2020-10-29 | 2023-07-28 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN116060116A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrodewaxing catalyst and preparation method and application thereof |
| CN116328852A (en) * | 2021-12-23 | 2023-06-27 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier and preparation method thereof |
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