CN103301888A - 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, particularly contain the preparation method of the wax oil hydrogenation pretreatment catalyst carrier of sial-phosphorus aluminium composite molecular screen.
Technical background
In the face of increasingly heaviness, the in poor quality of boundary stone oil resource, the increasingly high quality of petroleum fuel product, clean, thereby development heavy crude Efficient Conversion is bent the weight with the head that the clear gusoline production technology becomes current petrochemical processing industry.Catalytic cracking and hydrocracking technology are with heavy oil lighting important technical.The straight-run gas oil ratio reduces gradually in recent years catalytic cracking, the hydrocracking raw material, and high-sulfur nitrogen wax oil, decompression deep drawing wax oil, wax tailings and depitching wet goods component ratio inferior constantly increase, raw material is the increasingly trend of in poor quality, nitride in the raw material has great negative effect to catalyst activity and product quality, thereby forces Petrochemical Enterprises to add hydrogen pretreatment to catalytic cracking, hydrocracking wax oil raw material.The pretreated performance of hydrogenation directly affects the whole efficiency of catalytic cracking, hydrocracking process, becomes one of key core technology of catalytic cracking, hydrocracking.
The exploitation that focuses on catalyst of wax oil hydrogenation cracking preconditioning technique.Hydrogenation pretreatment catalyst is by carrier and active metal composition, and carrier is generally aluminium oxide, and active component is group vib and VIII family metal, metal oxide and metal sulfide.It is imperative that the weak core of alumina catalyst support acidity is to develop high activity wax oil hydrogenation pretreatment catalyst.It is carrier that hydrogenation pretreatment catalyst adopts aluminium oxide usually, but because the limitation of the aperture of aluminium oxide own and surface acidity, the polycyclic aromatic hydrocarbon that single catalyst as carrier preparation can not be realized the degree of depth saturated with the removing of heterocyclic nitrogen compound, need to carry out the modification of aluminium oxide.The interaction force between pore structure, surface acidity and adjustment carrier and the metal of carrier need to be improved in a new generation hydrogenation pretreatment catalyst exploitation aspect.
Chinese invention patent CN100469443C discloses a kind of hydrogenation catalyst, adopts SiO
2The modified aluminas surface increases Al
2O
3Surface acidity, improve the 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, increase the acidity of catalyst, improved the 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 the dipping active component, be prepared into catalyst, but add acid strong molecular sieve modified carrier, though increased the cracking activity of catalyst, but also increasing catalyst shows carbon deposition quantity, affects the long period stability operation of hydrotreating catalyst.Chinese invention patent CN1015915610A discloses a kind of diesel oil hydrofining catalyst that contains the one-dimensional channels molecular sieve, on the basis of the cracking that prevents diesel oil distillate, realize the hydrogenation of aromatic hydrocarbons saturated with deep removal sulphur, nitrogen compound.Chinese invention patent CN102019201A discloses a kind of preparation method who contains the heavy distillate Hydrobon catalyst of 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 jointly as carrier, by the synergy of two kinds of molecular sieves, improve the hydrofinishing performance of catalyst, make it process bad heavy distillate relaxing under the process conditions, reach deep desulfuration, denitrification effect.
Summarize described, saturated many epithios, nitride that the wax oil hydrogenation pretreatment catalyst mainly carries out polycyclic aromatic hydrocarbon remove, the hydrogenation of polycyclic aromatic hydrocarbon is saturated mainly at hydrogenation sites, the fracture of C-S, C-N key mainly occurs in acid centre, therefore requires hydrogenation pretreatment catalyst to need Proper Match hydrogenation sites and acid centre.Introduce the acid centre that molecular sieve can increase catalyst in the above technological invention patent in the disclosed hydrotreating catalyst, coordinate to carry out the removing of saturated and sulphur, nitrogen compound of polycyclic aromatic hydrocarbon with hydrogenation sites.Yet single introducing molecular sieve can not effectively mate acid site and hydrogenation center, needs comprehensively modifying carrier surface and latched position dipping reactive metal, could develop the high-activity hydrocracking pretreatment catalyst.
Summary of the invention
Weak point for above technology, the invention provides a kind of preparation method of wax oil hydrogenation pretreatment catalyst carrier, the method is introduced sial-phosphorus aluminium composite molecular screen not only can increase the acidity of carrier, can also regulate the alumina surface hydroxyl and distribute, and is conducive to the dispersion of reactive metal.Increased the density in II class activated centre with the hydrogenation pretreatment catalyst of carrier preparation of the present invention, the introducing of composite molecular screen, for catalyst provides the B acid site, the lytic activity of the saturated performance of hydrogenation of polycyclic aromatic hydrocarbon and C-S, C-N key has been improved in hydrogenation sites and the acid site of more reasonably mating catalyst.
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, mass percent by 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 take sial or modification Si-Al zeolite as nuclear; Described modified aluminas is to alumina modified gained by one or more elements in silicon, titanium, the zirconium; Described carrier specific area is 250 ~ 400 m
2/ g, pore volume are 0.50 ~ 0.80 cm
3/ g;
The preparation method that described wax oil hydrogenation is processed catalyst carrier may further comprise the steps:
1) sial-phosphorus aluminium composite molecular screen is synthetic: with phosphoric acid, boehmite and deionized water mix, add as required silicon source or modified metal soluble-salt, then add poly-N, N-two tetraethyl ammonium hydrochlorides, add at last template, stir and form even gel mixture system, described gel mixture is packed in the autoclave, after crystallization 2 ~ 8 H-shapeds become the phosphate aluminium molecular sieve crystal seed under 60 ~ 100 ℃ of temperature, add sial or modification Si-Al zeolite, hydro-thermal dynamic crystallization 12 ~ 48 h under 160 ~ 200 ℃ of temperature, with the crystallization products therefrom through separating, naturally dry, dry, obtain sial-phosphorus aluminium composite molecular screen after the roasting;
2) mixing in the former powder that the sial that step 1) is synthetic-phosphorus aluminium composite molecular screen and macroporous aluminium oxide, modified aluminas mix adds extrusion aid, then add expanding agent solubility solution and acidic mixed solution carries out kneading, extrusion modling, at last by the carrier that naturally dries, dry, roasting obtains hydrogenation pretreatment catalyst;
Wherein, boehmite in the described gel mixture system, phosphoric acid, template, modified metal soluble-salt, N, the mol ratio of N-two tetraethyl ammonium hydrochlorides 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 the 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 Si, Mg, Zn, Co, the element modified phosphate aluminium molecular sieve of Mn, Fe; Described Si-Al zeolite is preferably one or more among ZSM-5, Y after ZSM-5, Y, Beta, ZSM-22, ZSM-23 and the modification, Beta, ZSM-22, the ZSM-23;
In step 1), synthetic described AFI type phosphate aluminium molecular sieve template is triethylamine; Synthetic described AEL, ATO and AFO type phosphate aluminium molecular sieve template are 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 the active silica, and described Mg, Zn, Co, Mn and Fe modified metal salt are preferably one or more in solubility nitrate, sulfate, chlorate and the acetate; The baking temperature of described crystallization product is 120 ~ 180 ℃, behind dry 4 ~ 24 h, makes sial-phosphorus aluminium composite molecular screen behind 520 ~ 600 ℃ of roasting 2 ~ 12 h;
Step 2) in, described extrusion aid is that the 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, 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% that mixes 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 ℃, and be 6 ~ 36 h drying time, and dry rear temperature programming to 450 ~ 600 ℃ of roasting 2 ~ 12 h obtain catalyst carrier.
In technique scheme, described sial-phosphorus aluminium composite molecular screen specific area is 200 ~ 500 m
2/ g, pore volume are 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 are 0.60 ~ 0.90 cm
3/ g; Wherein total addition of modifying element oxide quality of accounting for modified aluminas is for 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, wherein most preferably is butterfly or tooth spherical.
The present invention compared with prior art, its beneficial effect is as follows:
Carrier of hydrogenating catalyst of the present invention with sial-phosphorus aluminium composite molecular screen, macroporous aluminium oxide and modified aluminas as raw material.Wherein component sial-phosphorus aluminium composite molecular screen is as nuclear take Si-Al zeolite or modification Si-Al zeolite, with phosphate aluminium molecular sieve or modification phosphorus aluminium zeolite, the phosphoric acid of introducing in its sieve synthesis procedure is not only as the synthetic phosphoric acid of phosphate aluminium molecular sieve, phosphoric acid also carries out modification to Si-Al zeolite simultaneously, and the acid amount of modulation zeolite distributes with acid.Sial-the introducing of phosphorus aluminium composite molecular screen not only can increase the acidity of carrier, can also regulate the alumina surface hydroxyl and distribute, and is conducive to the dispersion of reactive metal." AlPO4 " structure of crystal is conducive to suppress the formation of passive nickel aluminate, regulates the interaction force between metal and the carrier.Carrier of the present invention has increased the density in II class activated centre when the hydrogenation pretreatment catalyst of supported active preparation of metals, the introducing of composite molecular screen, for catalyst provides the B acid site, catalyst is improved to the cracking ability of the saturated performance of hydrogenation of polycyclic aromatic hydrocarbon and C-S, C-N key in hydrogenation sites and the acid site of more reasonably mating catalyst.After the carrier loaded reactive metal of wax oil hydrogenation pretreatment catalyst of the present invention is prepared into catalyst, can be applicable to the hydrogen pretreatment that adds of faulty wax oil, be adapted to especially the hydrogen pretreatment that adds of catalytic cracking, hydrocracking raw material.
The specific embodiment
The below describes technical characterstic of the present invention with specific embodiment, but is not limited only to this.
Embodiment-1
HY/AlPO
4Synthesizing of-5 composite molecular screens: with 109.0 g phosphoric acid (AR, mass concentration 85%) mixes in 35 ℃ 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 the poly-N of 4.0 g, N-two tetraethyl ammonium hydrochlorides (are called for short PCD, the pure Co., Ltd in road, Henan, purity 95%), slowly stir 0.5 h after, add 64.0 g triethylamines and (be called for short TEA, purity 99%), continue to stir 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 packed in the polytetrafluoroethylene (PTFE) autoclave, (behind lower aging 4 h of 1 ℃ of heating rate/min), obtain AlPO at 100 ℃
4Then-5 molecular sieve crystal seeds add 45.0 g HY molecular sieves (glad year auxiliary agent Co., Ltd in Shanghai, silica alumina ratio is 2.5), behind 185 ℃ of lower crystallization 24 h.Product after the crystallization is separated, and the gained solid matter with deionized water is washed to pH=7 ~ 8, at 120 ℃ of lower dry 12 h that process, obtains HY/AlPO
4The former powder of-5 composite molecular screens; Former powder (behind roasting 4 h of 2 ℃ of heating rates/min), is obtained HY/AlPO at 580 ℃
4-5 composite molecular screens.
Embodiment-2
Synthesizing of USY/SAPO-5 composite molecular screen: 109.0 g phosphoric acid and 306.0 g deionized waters are mixed in 35 ℃ of water-baths, add 60.0 g boehmites, constant temperature uniform stirring 0.5 h obtains aluminium phosphate sol; Add 4.0 g PCD, slowly stir 0.5 h after, add 16.0 g ethyl orthosilicates and (be called for short TEOS, purity 99%), then behind slow stirring 0.5 h, add 64.0 g TEA, continue to stir 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 packed in the polytetrafluoroethylene (PTFE) autoclave, (behind lower aging 8 h of 1 ℃ of heating rate/min), obtain SAPO-5 molecular sieve crystal seed, then add the glad year auxiliary agent Co., Ltd in 40.0 g USY(Shanghai at 90 ℃, silica alumina ratio is 12) molecular sieve, behind 185 ℃ of lower crystallization 24 h.Product after the crystallization is separated, and the gained solid matter with deionized water is washed to pH=7 ~ 8, at 120 ℃ of lower dry 8 h that process, obtains the former powder of USY/SAPO-5 composite molecular screen; Former powder (behind roasting 4 h of 2 ℃ of heating rates/min), is obtained the USY/SAPO-5 composite molecular screen at 580 ℃.
Embodiment-3
Beta/AlPO
4Synthesizing of-5 composite molecular screens: 114.0 g phosphoric acid and 306.0 g deionized waters are mixed in 35 ℃ of water-baths, add 60.0 g boehmites, constant temperature uniform stirring 0.5 h obtains aluminium phosphate sol; Add 4.0 g PCD, stir slow 0.5 h after, add 64.0 g TEA, continue to stir 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 packed in the polytetrafluoroethylene (PTFE) autoclave, (behind lower aging 4 h of 1 ℃ of heating rate/min), obtain AlPO at 100 ℃
4Then-5 molecular sieve crystal seeds add 45.0 g Beta molecular sieves (glad year auxiliary agent Co., Ltd in Shanghai, silica alumina ratio is 24), behind 175 ℃ of lower crystallization 36 h.Product after the crystallization is separated, and the gained solid matter with deionized water is washed to pH=7 ~ 8, at 120 ℃ of lower dry 8 h that process, obtains Beta/AlPO
4The former powder of-5 composite molecular screens; Former powder (behind roasting 6 h of 2 ℃ of heating rates/min), is obtained Beta/AlPO at 550 ℃
4-5 composite molecular screens.
Embodiment-4
Synthesizing of USY/SAPO-11 composite molecular screen: 120.0 g phosphoric acid and 320.0 g deionized waters are mixed in 38 ℃ of water-baths, add 65.0 g boehmites, magnetic agitation 0.5 h obtains aluminium phosphate sol in 38 ℃ of water-baths; Add 6.0 g PCD, slowly stir 0.5 h after, add 16.0 g TEOS, after continuing to stir 0.5 h, add 72.0 di-n-propylamines (being called for short TEA, purity 98%), continue to stir 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 packed in the polytetrafluoroethylene (PTFE) autoclave, (behind lower aging 4 h of 1 ℃ of heating rate/min), obtain the SAPO-11 crystal seed, then add 50.0 g USY molecular sieves, behind 180 ℃ of lower crystallization 24 h at 100 ℃.Product after the crystallization is separated, and the gained solid matter with deionized water is washed to pH=7 ~ 8, at 120 ℃ of lower dry 12 h that process, obtains the former powder of USY/SAPO-11 composite molecular screen; Former powder (behind roasting 4 h of 2 ℃ of heating rates/min), is obtained the USY/SAPO-11 composite molecular screen at 600 ℃.
Embodiment-5
Synthesizing of Beta/CoAPO-5 composite molecular screen: 109.0 g phosphoric acid (AR, 85%) and 306.0 g deionized waters are mixed in 38 ℃ of water-baths, add 60.0 g boehmites, constant temperature uniform stirring 0.5 h obtains aluminium phosphate sol; Add 6.0 g PCD, slowly stir 0.5 h after, add 24.0 g cobalt acetates, after slowly stirring 0.5 h, add 64.0 g triethylamines and (be called for short TEA, AR, 99%), continue to stir 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 packed in the polytetrafluoroethylene (PTFE) autoclave, at 90 ℃ of (behind lower aging 4 h of 1 ℃ of heating rate/min), obtain the CoAPO-5 crystal seed, then add 40.0 g Beta(silica alumina ratios 24) molecular sieves, behind 190 ℃ of lower crystallization 36 h.Product after the crystallization is carried out centrifugation, and the gained solid matter with deionized water is washed to pH=7 ~ 8, at 120 ℃ of lower dry 12 h that process, obtains the former powder of Beta/CoAPO-5 composite molecular screen; Former powder (behind roasting 4 h of 2 ℃ of heating rates/min), is obtained the Beta/CoAPO-5 composite molecular screen at 580 ℃.
Embodiment-6
With 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 silicon 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 and mix former powder.With 120 g by deionized water (92wt%) and soluble starch (8wt%, the color Fine Chemical Co., Ltd of Langfang roc, purity 99.8%) the expanding agent solution of preparation is mixed in the former powder by disposable the pouring into of acid solution of water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) preparation with 200.0 g, elder generation's kneading is to squeezing paste, be that 8 mm column type orifice plates respectively push once through hollow plate, diameter again, being extruded at last diameter is the butterfly bar of 1.8 mm; The wet bar of gained is dried naturally, and dry 6 h in 120 ℃ of baking ovens are placed at last the Muffle furnace Program and are warming up to 550 ℃ of roasting 4 h again, namely obtain carrier S ZT-1.
Embodiment-7
With 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 and mix former powder.100 g are mixed in the former powder by disposable the pouring into of acid solution of water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) preparation with 200.0 g with the expanding agent solution of soluble starch (8wt%) preparation by deionized water (92wt%), elder generation's kneading is to squeezing paste, be that 8 mm column type orifice plates respectively push once through hollow plate, diameter again, being extruded at last diameter is the butterfly shape bar of 1.8 mm; The wet bar of gained is dried naturally, and dry 6 h in 120 ℃ of baking ovens are placed at last the Muffle furnace Program and are warming up to 550 ℃ of roasting 4 h again, namely obtain carrier S ZT-2.
Embodiment-8
With 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 and mix former powder.With 120 g by deionized water (92wt%) and polyethylene glycol (8wt%, Tianjin chemical reagent supply and marketing company, purity 99.0%) the expanding agent solution of preparation is mixed in the former powder by disposable the pouring into of acid solution of water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) preparation with 200.0 g, elder generation's kneading is to squeezing paste, be that 8 mm column type orifice plates respectively push once through hollow plate, diameter again, being extruded at last diameter is the butterfly bar of 1.8 mm; The wet bar of gained is dried naturally, and dry 6 h in 120 ℃ of baking ovens are placed at last the Muffle furnace Program and are warming up to 550 ℃ of roasting 4 h again, namely obtain carrier S ZT-3.
Embodiment-9
With 180.0 g macroporous aluminium oxides, 80.0 g AlPO
4-5/Beta composite molecular screen (contents on dry basis 93%), 125.0 g silicon modified aluminas, 12.0 g sesbania powder and 6.0 g methylcellulose drop into kneading machine mixed grind 15 min after mixing, be mixed with and mix former powder.120 g are mixed in the former powder by disposable the pouring into of acid solution of water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) preparation with 200.0 g with the expanding agent solution of polyethylene glycol (10wt%) preparation by deionized water (90wt%), elder generation's kneading is to squeezing paste, be that 8 mm column type orifice plates respectively push once through hollow plate, diameter again, being extruded at last diameter is the butterfly bar of 1.8 mm; The wet bar of gained is dried naturally, and dry 6 h in 120 ℃ of baking ovens are placed at last the Muffle furnace Program and are warming up to 550 ℃ of roasting 4 h again, namely obtain carrier S ZT-4.
Embodiment-10
With 200.0 g macroporous aluminium oxides, 95.0 g SAPO-11/USY composite molecular screens (contents on dry basis 94%), 80.0 g silicon modified aluminas, 12.0 g sesbania powder and 6.0 g methylcellulose, drop into kneading machine mixed grind 15 min after mixing, be mixed with and mix former powder.120 g are mixed in the former powder by disposable the pouring into of acid solution of water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) preparation with 200.0 g with the expanding agent solution of soluble starch (10wt%) preparation by deionized water (90wt%), elder generation's kneading is to squeezing paste, be that 8 mm column type orifice plates respectively push once through hollow plate, diameter again, being extruded at last diameter is the butterfly bar of 1.8 mm; The wet bar of gained is dried naturally, and dry 6 h in 120 ℃ of baking ovens are placed at last the Muffle furnace Program and are warming up to 550 ℃ of roasting 4 h again, namely obtain carrier S ZT-5.
Embodiment-11
With 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 and mix former powder.120 g are mixed in the former powder by disposable the pouring into of acid solution of water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) preparation with 200.0 g with the expanding agent solution of polyethylene glycol (10wt%) preparation by deionized water (90wt%), elder generation's kneading is to squeezing paste, be that 8 mm column type orifice plates respectively push once through hollow plate, diameter again, being extruded at last diameter is the butterfly bar of 1.8 mm; The wet bar of gained is dried naturally, and dry 6 h in 120 ℃ of baking ovens are placed at last the Muffle furnace Program and are warming up to 550 ℃ of roasting 4 h again, namely obtain carrier S ZT-6.
Comparative example-1
With 250.0 g macroporous aluminium oxides, 6.0 g sesbania powder and 3.0 g methylcellulose, drop into kneading machine mixed grind 15 min after mixing, be mixed with and mix former powder.240.0 g is mixed in the former powder by disposable the pouring into of the acid solution of water (90wt%), nitric acid (4wt%), citric acid (3wt%), tartaric acid (3wt%) preparation, elder generation's kneading is to squeezing paste, be that 8 mm column type orifice plates respectively push once through hollow plate, diameter again, being extruded at last diameter is the butterfly bar of 1.8 mm; The wet bar of gained is dried naturally, and dry 6 h in 120 ℃ of baking ovens are placed at last the Muffle furnace Program and are warming up to 550 ℃ of roasting 4 h again, namely obtain carrier DSZT-1.
Embodiment-12
The preparation of Ni-Mo maceration extract: get the 180.0 g molybdenum trioxides (Bond of Jiangyan City, Jiangsu metal product plant, purity 99.8%), 60.0 g basic nickel carbonates (the new light fine chemistry industry in Fushun City Co., Ltd, purity 99.8%) and 9.0 g citric acids put into there-necked flask, add 120 mL deionized waters, add thermal agitation, slowly splash into 22.5 g phosphoric acid (mass concentration 85%), 100 ℃ are stirred 2 h, add deionized water fully after the dissolving volume of maceration extract be settled to 300 mL, make final maceration extract in the concentration of each oxide be: MoO
360g/100 mL, NiO 12g/100 mL, P
2O
54g/100 mL, the pH value of maceration extract is 1.6.
Get in example carrier S ZT-2, SZT-3, each 65.0 g placement dipping tank of SZT-5 comparison example DHZT-1 carrier, pour the above-mentioned maceration extract of certain volume into, after flooding 2 h, carrier behind the dipping is dried naturally, dry 8 h in 120 ℃ of baking ovens, be placed at last the Muffle furnace Program and be warming up to 480 ℃ of roasting 4 h, namely obtain wax oil hydrogenation pretreatment catalyst SHC-2, SHC-3, SHC-5, DHC-1.
The physico-chemical property of the hydrogenation pretreatment catalyst carrier of table-1 embodiment and comparison example preparation
The physico-chemical property of the hydrogenation pretreatment catalyst of table-2 embodiment and comparison example preparation
Data can be found out from table, introduce the total acid content that composite molecular screen and modified aluminas can improve catalyst in the carrier, and the B acid site of having improved especially catalyst is conducive to the fracture of catalyst saturated and C-S, C-N key to the hydrogenation of polycyclic aromatic hydrocarbon.
Embodiment-13
The present embodiment is introduced by the pretreating catalyst by hydrocracking of the present invention's preparation and comparative catalyst's activity rating.Estimate on 200 mL fixed bed hydrogenation reaction units, its reaction condition is: reaction temperature is 380 ℃, reaction pressure 10.0 MPa, hydrogen to oil volume ratio 800:1, volume space velocity 1.5 h
-1, its evaluation result is shown in table-3.
Table-3 take carrier of the present invention as basis preparation catalyst and the comparative catalyst add the hydrogen pretreatment performance
* relative denitrification activity=ln (S
Tol/ S
C)/ln (S
Tol/ S
DC) * 100, wherein S
TolBe the total sulfur in the feedstock oil, S
DCBe the sulfur content in comparative catalyst's hydrogenation products, S
CBe the sulfur content in other catalyst hydrogenation products;
Relative denitrification activity=ln (the N of *
Tol/ N
C)/ln (N
Tol/ N
DC) * 100, wherein N
TolBe the total nitrogen in the feedstock oil, N
DCBe the nitrogen content in comparative catalyst's hydrogenation products, N
CBe the nitrogen content in other catalyst hydrogenation products.
After the carrier loaded reactive metal of hydrogenation pretreatment catalyst of the inventive method preparation is prepared into catalyst, can be applicable to the hydrogen pretreatment that adds of faulty wax oil, be adapted to especially the hydrogen pretreatment that adds of catalytic cracking, hydrocracking raw material, usually hydrotreatment, the pretreated process regulation of hydrogenation are: reaction temperature is 360～400 ℃, 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, mass percent by 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 take sial or modification Si-Al zeolite as nuclear; Described modified aluminas is to alumina modified gained by one or more elements in silicon, titanium, the zirconium; Described carrier specific area is 250 ~ 400 m
2/ g, pore volume are 0.50 ~ 0.80 cm
3/ g;
The preparation method that described wax oil hydrogenation is processed catalyst carrier may further comprise the steps:
1) sial-phosphorus aluminium composite molecular screen is synthetic: with phosphoric acid, boehmite and deionized water mix, add as required silicon source or modified metal soluble-salt, then add poly-N, N-two tetraethyl ammonium hydrochlorides, add at last template, stir and form even gel mixture system, described gel mixture is packed in the autoclave, after crystallization 2 ~ 8 H-shapeds become the phosphate aluminium molecular sieve crystal seed under 60 ~ 100 ℃ of temperature, add sial or modification Si-Al zeolite, hydro-thermal dynamic crystallization 12 ~ 48 h under 160 ~ 200 ℃ of temperature, with the crystallization products therefrom through separating, naturally dry, dry, obtain sial-phosphorus aluminium composite molecular screen after the roasting;
2) mixing in the former powder that the sial that step 1) is synthetic-phosphorus aluminium composite molecular screen and macroporous aluminium oxide, modified aluminas mix adds extrusion aid, then add expanding agent solubility solution and acidic mixed solution carries out kneading, extrusion modling, at last by the carrier that naturally dries, dry, roasting obtains hydrogenation pretreatment catalyst;
Wherein, boehmite in the described gel mixture system, phosphoric acid, template, modified metal soluble-salt, N, the mol ratio of N-two tetraethyl ammonium hydrochlorides 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 the 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 Si, Mg, Zn, Co, the element modified phosphate aluminium molecular sieve of Mn, Fe; Described Si-Al zeolite is ZSM-5, Y, Beta, the ZSM-22 after ZSM-5, Y, Beta, ZSM-22, ZSM-23 and the modification, one or more among the ZSM-23;
In step 1), synthetic described AFI type phosphate aluminium molecular sieve template is triethylamine; Synthetic described AEL, ATO and AFO type phosphate aluminium molecular sieve template are 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 the active silica, and described modified metal salt comprises one or more in solubility nitrate, sulfate, chlorate and the acetate of Mg, Zn, Co, Mn and Fe; The baking temperature of described crystallization product is 120 ~ 180 ℃, behind dry 4 ~ 24 h, makes sial-phosphorus aluminium composite molecular screen behind 520 ~ 600 ℃ of roasting 2 ~ 12 h;
Step 2) in, described extrusion aid is that the 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, 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% that mixes 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 ℃, and be 6 ~ 36 h drying time, and dry rear temperature programming to 450 ~ 600 ℃ of roasting 2 ~ 12 h obtain catalyst carrier.
3. method according to claim 1 is characterized in that, described sial-phosphorus aluminium composite molecular screen specific area is 200 ~ 500 m
2/ g, pore volume are 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.
4. method according to claim 1 is characterized in that, the specific area of described modified aluminas is 300 ~ 450 m
2/ g, pore volume are 0.60 ~ 0.90 cm
3/ g; Wherein total addition of modifying element oxide quality of accounting for modified aluminas is for 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 used at the faulty wax oil hydrogenation pretreatment catalyst, the control process conditions are: reaction temperature is 360～400 ℃, reaction pressure 8.0～12.0 MPa, hydrogen to oil volume ratio 600:1 ~ 1000:1, volume space velocity 1.0 ~ 2.0h
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