CN105709851A - preparation method of aluminium oxide-based carrier containing silicon and boron - Google Patents
preparation method of aluminium oxide-based carrier containing silicon and boron Download PDFInfo
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- CN105709851A CN105709851A CN201410715680.5A CN201410715680A CN105709851A CN 105709851 A CN105709851 A CN 105709851A CN 201410715680 A CN201410715680 A CN 201410715680A CN 105709851 A CN105709851 A CN 105709851A
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Abstract
The invention discloses a preparation method of an aluminium oxide-based carrier containing silicon and boron. The preparation method comprises following steps: water soluble silicone oil and a soluble boron-containing compound are introduced into an aluminium oxide-based carrier successively or simultaneously, and the aluminium oxide-based carrier containing silicon and boron is obtained via heat treatment. The preparation method is capable of adjusting distribution of acid centers and hydrogenation active centers, achieving coordination effects, and improving catalyst performance; and the modified aluminium oxide-based carrier is suitable to be taken as a hydrogenation catalyst carrier.
Description
Technical field
The preparation method that the present invention relates to a kind of siliceous alumina-based supports with boron, is particularly well-suited to the carrier of hydrodenitrogenation catalyst.
Background technology
Loaded catalyst majority adopts infusion process to prepare, for instance various hydrogenation catalysts.Aluminium oxide is frequently as the carrier material of such catalyst.But pure Al2O3Active metal on surface is relatively big with the interaction force of carrier, is easily formed inactive species (as formed nickel aluminate), and not easily complete cure forms the II type activity phase with high hydrogenation activity.Simultaneously, the activity of hydrogenation catalyst is had considerable influence by catalyst surface Acidity, hetero atom in elimination raw material, catalyst is needed to have hydrogenolysis activity, this is to occur on the acid centre of catalyst, therefore, how to weaken the strong interaction of metal and carrier, how to make catalyst have suitable acidity, become key prepared by high-activity hydrogenation catalyst.A lot of character of catalyst are determined by carrier, thus developing suitable carrier is one of key factor developing catalyst.
At present, the method that alumina support is modified is a lot, wherein introduce auxiliary agent such as silicon, phosphorus, fluorine, boron, zirconium, titanium, magnesium, gallium, vanadium, manganese, copper, zinc etc., can be used to improve the character of alumina support, but it is different with mode owing to introducing the consumption of auxiliary agent, kind, making the different in kind of alumina support, even difference is very big.
CN00110018.1 discloses a kind of hydrogenation catalyst and preparation method thereof, this catalyst is with group VIB and VIII race's metal for hydrogenation active component, auxiliary agent is fluorine, supporting the one in boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium simultaneously or it is mixed into auxiliary agent, its key problem in technology is to adopt coprecipitation to prepare.
The preparation method that CN200910236166.2 discloses a kind of catalyst for hydrorefining pertroleum wax.The method includes: weigh boehmite, adds the silicon-containing compound of 6%～17% and the organic phosphorus compound solution of 2%～20%, extruded moulding on banded extruder, drying and roasting, prepares siliceous and phosphorus γ-Al2O3Carrier；Silicon-containing compound is SiO2The Ludox of weight concentration 30% or nano silicon.
Above-mentioned prior art is with coprecipitation or adds auxiliary agent when molding, the former can cause the auxiliary agent such as active metal and Si to enter body phase in coprecipitation process, and many kinds of substance precipitates simultaneously, identical deposition condition can not be the best deposition condition of many kinds of substance simultaneously, and the formation of active metal activity phase and the acid adjustment effect of catalyst are not had selectivity by auxiliary agent, thus affecting the combination property of final catalyst；And the latter adds the auxiliary agents such as Si when kneading and compacting, being unfavorable for that auxiliary agent is dispersed, not only the utilization rate of auxiliary agent reduces, and the acidity and active equal comprehensive adjustment effect to catalyst is more weak, is unfavorable for the raising of catalyst combination property.
Summary of the invention
For the deficiencies in the prior art, the preparation method that the present invention provides a kind of siliceous alumina-based supports with boron.The method can regulate the distribution of acid centre and hydrogenation sites so that it is mutually coordinated effect, improves the performance of catalyst, and this modified oxidized alumina-based support is suitable to carrier of hydrogenating catalyst.
The preparation method of the siliceous alumina-based supports with boron of the present invention, including: water-soluble silicon oil and solubility boron-containing compound are sequentially or simultaneously introduced alumina-based supports, after Overheating Treatment, prepares siliceous and boron alumina-based supports.
In the inventive method, water-soluble silicon oil introduce the silicone content in carrier and account for the 0.1%～5.0% of modified oxidized alumina-based support weight in silicon dioxide, it is preferred to 0.2%～2.0%, more preferably 0.2% ~ 0.9%.
In the inventive method, solubility boron-containing compound introduce the Boron contents in carrier and account for the 0.1%～10.0% of modified oxidized alumina-based support weight in diboron trioxide, it is preferred to 0.3%～6.0%, more preferably 0.5% ~ 3.0%.
In the inventive method, introduce mol ratio that the consumption of water-soluble silicon oil and solubility boron-containing compound counts with silicon oxide and boron oxide respectively for 0.02 ~ 40.0, it is preferred to 0.04 ~ 10.0, more preferably 0.1 ~ 2.0.
Water-soluble silicon oil described in the inventive method, refers to be dissolved in the silicone oil of water, it is preferable that character is as follows: viscosity when 25 DEG C is 200 ~ 7000mPa.s, it is preferred to 500 ~ 5000mPa.s, and cloud point is 30 ~ 100 DEG C, it is preferred to 40 ~ 65 DEG C.Described water-soluble silicon oil is usually and adopts the method for group modified silicone oil to obtain, such as polyether modified silicon oil.
Alumina-based supports of the present invention refers to aluminium oxide for key component, can without adjuvant component, can also containing adjuvant component, wherein adjuvant component can be one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component content in alumina-based supports is at below 30wt%, preferred below 20wt%, more preferably below 15wt%.Alumina-based supports used in the present invention is that aluminium hydroxide (such as boehmite) obtains after high-temperature roasting, and the condition of high-temperature roasting is as follows: at 450 DEG C～1000 DEG C roasting 1.0h～20.0h, it is preferred to 3.0h ~ 8.0h.Described alumina-based supports can adopt conventional method to prepare, and the needs according to practical application, it is possible to make shaping carrier obtain alumina-based supports then through high-temperature roasting after aluminium hydroxide molding.The shape of carrier can make the suitable shapes such as spherical, bar shaped (such as Herba Trifolii Pratentis, Herba Galii Bungei or cylindrical bars) as required, can add conventional shaping assistant, such as extrusion aid, peptization acid, binding agent etc. in forming process.The character of described alumina-based supports is as follows: specific surface area is 120 ~ 420m2/ g, it is preferred to 220 ~ 320m2/ g；Pore volume is 0.4 ~ 1.3mL/g, it is preferred to 0.6 ~ 1.0mL/g；Bore dia accounts for less than the 20% of total pore volume less than the pore volume shared by the hole of 4nm, it is preferable that account for less than 10%, and more preferably less than 5%.
In the inventive method, solubility boron-containing compound refers to the combination of one or more in boric acid, ammonium pentaborate, tetraboric acid ammonium etc..
In the inventive method, water-soluble silicon oil and solubility boron-containing compound successively or are simultaneously introduced on carrier, can first be incorporated on carrier by water-soluble silicon oil, are then incorporated on carrier by solubility boron-containing compound again；Or being simultaneously introduced on carrier by water-soluble silicon oil and solubility boron-containing compound, its incorporation way adopts infusion process, and infusion process can be incipient impregnation, it is also possible to be excessive dipping；Can be repeatedly impregnate, it is also possible to be single-steeping.For improving efficiency, it is preferred to adopt an equal-volume co-impregnation.
In the inventive method, described heat treatment adopts two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, being preferably 90 DEG C～120 DEG C, the process time is 0.5h～20.0h, it is preferred to 1.0h～6.0h, second segment is 180 DEG C～400 DEG C in temperature, being preferably 200 DEG C～350 DEG C, the process time is 0.5h～20.0h, it is preferred to 1.0h～6.0h.Heat treatment can carry out in oxygen-containing atmosphere, oxygen concentration is not particularly limited, such as air atmosphere etc., it is also possible to carries out in an inert atmosphere, such as nitrogen atmosphere etc..
Modified oxidized alumina-based support prepared by the inventive method, with a small amount of specific water-soluble silicon oil oxide impregnation alumina-based support, the effect utilizing the hydrophilic of water-soluble silicon oil and hydrophobic group makes it load on the ad-hoc location on alumina-based supports surface, and make the boron-containing compound simultaneously or afterwards impregnated evenly spread to around silica group, by suitable heat treatment, the Si of institute's load, B energy better coordinative role, form, at carrier surface ad-hoc location, the silicone hydroxyl being more evenly distributed to match with boron, carrier surface is made to form more acid suitable acid centre on the one hand, and match with the former acidic site of carrier surface, the acidity and the acid distribution that make carrier are more reasonable, on the other hand, be conducive to regulating the distribution of the hydrogenation sites of the active metal formation of follow-up load, and the cooperation of the acid centre of hydrogenation sites and carrier surface, thus improving the serviceability of catalyst.
Modified oxidized alumina-based support prepared by the inventive method, suitable to hydrotreating catalyst, the particularly carrier of hydrogenation removing impurities matter (such as sulfur, nitrogen etc.) catalyst, especially hydrodenitrogenationactivity activity increase rate is bigger.
Detailed description of the invention
In the present invention, cloud point refers to and stops heating after the water-soluble silicon oil solution that mass concentration is 1% is heated to muddiness, the lower temperature observed when aqueous solution is become limpid by muddiness of stirring.
According to the preparation method of modified oxidized alumina-based support provided by the invention, it specifically can adopt following steps:
1, solubility boron-containing compound being configured to solution A, wherein boron-containing compound concentration is calculated as 0.1g/100mL ~ 20g/100mL with boron oxide；
2, water-soluble silicon oil being configured to solution B, wherein water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/100mL with silicon oxide；
3, solubility boron-containing compound and water-soluble silicon oil being hybridly prepared into solution C, wherein boron-containing compound concentration is calculated as 0.1g/100mL ~ 10g/100mL with boron oxide, and water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 10g/100mL with silicon oxide；
4, at least following a kind of mode is adopted to guide in alumina-based supports by water-soluble silicon oil and boron-containing compound:
I, use solution C oxide impregnation alumina-based support, after health preserving, by two sections of heat treatments, obtain modified oxidized alumina-based support；Wherein in two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, it is preferably 90 DEG C～120 DEG C, the process time is 0.5h～20.0h, being preferably 1.0h～6.0h, second segment is 180 DEG C～400 DEG C in temperature, it is preferred to 200 DEG C～350 DEG C, the process time is 0.5h～20.0h, it is preferred to 1.0h～6.0h；
II, use solution B oxide impregnation alumina-based support, after health preserving, by Low Temperature Heat Treatment, then dipping solution A, after health preserving, by two sections of heat treatments, obtain modified oxidized alumina-based support；Wherein Low Temperature Heat Treatment is at 60 DEG C～150 DEG C, it is preferred to 90 DEG C～120 DEG C, the process time is 0.5h～20.0h, it is preferred to 1.0h～6.0h；In two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, it is preferably 90 DEG C～120 DEG C, the process time is 0.5h～20.0h, being preferably 1.0h～6.0h, second segment is 180 DEG C～400 DEG C in temperature, it is preferred to 200 DEG C～350 DEG C, the process time is 0.5h～20.0h, it is preferred to 1.0h～6.0h.
In the inventive method, heat treatment can carry out in oxygen-containing atmosphere, oxygen concentration is not particularly limited, such as air atmosphere etc., it is also possible to carries out in an inert atmosphere, such as nitrogen atmosphere etc..
Conditioned time after dipping solution is not specifically limited by the inventive method, conditioned time is as the criterion with the uniform adsorption that can guarantee that water-soluble silicon oil and boron-containing compound component, those skilled in the art can judge according to the absorption situation of the viscosity situation of solution and solution, determines conditioned time.
The technical scheme that the invention is further illustrated by the following examples, but invention should not be deemed limited in this embodiment.In the present invention, wt% is mass fraction, without specified otherwise, is air atmosphere.
In the present invention, raw oil and the sulfur content S(wt% in hydrotreatment products) adopt ultraviolet fluorescence method (SH/T0689-2000) to record, nitrogen content N(μ g/g) adopt boat sample introduction chemoluminescence method (SH/T0704-2001) to record.
In the embodiment of the present invention and comparative example, the hydrodesulfurization activity of catalyst presses 1.7 grades of calculating, and hydrodenitrogenationactivity activity presses 1 grade of calculating, and sulfur content unit when hydrodesulfurization activity calculates is μ g/g, nitrogen content unit when hydrodenitrogenationactivity activity calculates is μ g/g, and circular is as follows:
Hydrodesulfurization activity=1/ (in product sulfur content)0.7-1/ (in raw material sulfur content)0.7
Hydrodenitrogenationactivity activity=ln [in raw oil nitrogen content in nitrogen content/product]
Embodiment hydrodesulfurization activity relative to the catalyst of comparative example and relative hydrodenitrogenationactivity activity in the present invention, it is all using the hydrodesulfurization activity of catalyst DT6 and hydrodenitrogenationactivity activity as reference, the relative hydrodesulfurization activity of catalyst DT6 is designated as 100%, and the relative hydrodenitrogenationactivity activity of catalyst DT6 is designated as 100%；
The relative hydrodesulfurization activity of other catalyst is:
(hydrodesulfurization activity of the hydrodesulfurization activity ÷ catalyst DT6 of this catalyst) × 100%；
The relative denitrification activity of other catalyst is:
(hydrodenitrogenationactivity activity of the hydrodenitrogenationactivity activity ÷ catalyst DT6 of this catalyst) × 100%.
In embodiment, water-soluble silicon oil A used is produced by Qingdao industrial organosilicon new material company, SiO2Content is 15wt%, and viscosity (25 DEG C) 1500 ~ 5000mPa.s, cloud point is 47 DEG C；Water-soluble silicon oil B is produced along bright Chemical Co., Ltd. by Laiyang, SiO2Content is 9wt%, and viscosity (25 DEG C) is 500～1500mPa.s, and cloud point is 45～55 DEG C；Water-soluble silicon oil C is produced by Laiyang Sheng Bang organosilicon Science and Technology Ltd.,SiO2Content is 30wt%, and viscosity (25 DEG C) is 600～5000mPa.s, and cloud point is 42～46 DEG C.
In embodiment and comparative example, the pore structure of aluminum hydroxide solid elastomer powder used is as shown in table 1:
The pore structure of aluminum hydroxide solid elastomer powder used in table 1 embodiment and comparative example
| Project | SB powder | Macropore aluminum hydroxide solid elastomer powder |
| Specific surface area, m2/g | 239 | 316 |
| Pore volume, mL/g | 0.53 | 1.18 |
| Pore size distribution, % | ||
| < 4nm | 4.4 | 1.0 |
| 4~8nm | 78.5 | 14.6 |
| 8~15nm | 15.3 | 34.1 |
| > 15nm | 1.8 | 50.3 |
Embodiment 1
Take macropore aluminum hydroxide solid elastomer powder 3800g, SB powder 200g, add citric acid and each 160g of sesbania powder, mix homogeneously.Then being uniformly added into diluted nitric acid aqueous solution 2900g, wherein concentration of nitric acid is 2.9wt%.By material kneading 15min, then roll 20min, by the Herba Trifolii Pratentis orifice plate extrusion of diameter 1.7mm.500 DEG C of roasting 4h after 120 DEG C of dry 4h.Carrier after roasting is designated as Z.
The physico-chemical property of alumina support Z is as shown in table 2:
The physico-chemical property of table 2 alumina support Z
| Project | Alumina support Z |
| Specific surface area, m2/g | 293 |
| Pore volume, mL/g | 0.66 |
| Pore size distribution, % | |
| < 4nm | 3.1 |
| 4~8nm | 60.9 |
| 8~15nm | 31.7 |
| > 15nm | 4.3 |
| Infrared total acid, mmol/g | 0.409 |
| Bulk density, g/100mL | 62 |
| Saturated liquid absorption, mL/100g | 78 |
Embodiment 2
Weighing tetraboric acid ammonium 7.5g, add appropriate amount of deionized water and dissolve, making volume is 105mL, obtained solution A1.Weighing water-soluble silicon oil A16.5g, add appropriate amount of deionized water and dissolve, making volume is 105mL, obtained solution B1.Under stirring, being poured slowly in 35mLA1 solution by 35mLB1 solution, and add appropriate amount of deionized water, making final volume is 78mL, is configured to C1 solution.
Take 100g alumina support Z, solution C 1 is uniformly sprayed on the alumina support, after health preserving 10 hours, through 105 DEG C of heat treatment 3h, 230 DEG C of heat treatment 2h, obtain modified carrier S 1.
35mL solution B 1 is diluted to 78mL with deionized water, uniformly it is sprayed on alumina support Z, health preserving 10 hours, after 100 DEG C of heat treatment 2h, then 35mLA1 solution deionized water is diluted to 76mL, uniformly sprays on this carrier, after health preserving 3 hours, through 105 DEG C of heat treatment 3h, 230 DEG C of heat treatment 2h, obtain modified carrier S 2.
Embodiment 3
Weighing boric acid 1.8g, water-soluble silicon oil B16.0g, add appropriate amount of deionized water and dissolve, making volume is 78mL, obtained solution C2.
Take 100g alumina support Z, solution C 2 is uniformly sprayed on the alumina support, after health preserving 10 hours, through 100 DEG C of heat treatment 2h, 220 DEG C of heat treatment 2h, obtain modified carrier S 3.
Weighing tetraboric acid ammonium 1.7g, boric acid 1.8g, water-soluble silicon oil B16.0g, add appropriate amount of deionized water and dissolve, making volume is 78mL, obtained solution C3.
Take 100g alumina support Z, solution C 3 is uniformly sprayed on the alumina support, after health preserving 10 hours, in a nitrogen atmosphere, through 100 DEG C of heat treatment 2h, 350 DEG C of heat treatment 2h, obtain modified carrier S 4.
Embodiment 4
Weighing boric acid 1.8g, water-soluble silicon oil C1.7g, add appropriate amount of deionized water and dissolve, making volume is 78mL, obtained solution C3.
Take 100g alumina support Z, solution C 3 is uniformly sprayed on the alumina support, after health preserving 10 hours, through 110 DEG C of heat treatment 2h, 260 DEG C of heat treatment 3h, obtain modified carrier S 5.
Embodiment 5
Weighing ammonium pentaborate 6.8g, water-soluble silicon oil C9.0g, add appropriate amount of deionized water and dissolve, making volume is 78mL, obtained solution C4.
Take 100g alumina support Z, solution C 4 is uniformly sprayed on the alumina support, after health preserving 10 hours, through 110 DEG C of heat treatment 2h, 260 DEG C of heat treatment 3h, obtain modified carrier S 6.
Comparative example 1
Take macropore aluminum hydroxide solid elastomer powder 190g, SB powder 10g, add citric acid and each 8g of sesbania powder, mix homogeneously.Weighing water-soluble silicon oil B24.0g, tetraboric acid ammonium 2.6g, boric acid 2.7g, be subsequently adding in aqueous solution of nitric acid, after stirring, obtain 155g acid solution, wherein concentration of nitric acid is 2.7wt%.By material kneading 15min, then roll 20min, by the Herba Trifolii Pratentis orifice plate extrusion of diameter 1.7mm.500 DEG C of roasting 4h after 120 DEG C of dry 4h.Carrier after roasting is designated as DS1.
Comparative example 2
Weighing water-soluble silicon oil A5.5g, add appropriate amount of deionized water and dissolve, making volume is 78mL, obtained solution B2.Take 100g alumina support Z, solution B 2 is uniformly sprayed on the alumina support, after health preserving 10 hours, through 105 DEG C of heat treatment 3h, 230 DEG C of heat treatment 2h, obtain modified carrier DS2.
Comparative example 3
Weighing tetraboric acid ammonium 7.5g, add appropriate amount of deionized water and dissolve, making volume is 78mL, is configured to A2 solution.Take 100g alumina support Z, solution A 2 is uniformly sprayed on the alumina support, after health preserving 10 hours, through 105 DEG C of heat treatment 3h, 230 DEG C of heat treatment 2h, obtain modified carrier DS3.
Comparative example 4
Compared with the preparation method of carrier S 2 in embodiment 2, this comparative example is first to introduce aluminium salt, introduces water-soluble silicon oil afterwards, and detailed process is as follows:
Take 100g alumina support Z, 35mLA1 solution deionized water is diluted to 78mL, uniformly spray on this carrier, after health preserving 3 hours, through 100 DEG C of heat treatment 2h, again 35mL solution B 1 is diluted to 76mL with deionized water, uniformly being sprayed on carrier Z, health preserving 10 hours, through 105 DEG C of heat treatment 3h, 230 DEG C of heat treatment 2h, obtain modified carrier DS4.
Comparative example 5
Weighing boric acid 2.0g, water-soluble silicon oil C45.5g, add appropriate amount of deionized water and dissolve, making volume is 78mL, obtained solution C5.
Take 100g alumina support Z, solution C 5 is uniformly sprayed on the alumina support, after health preserving 10 hours, through 110 DEG C of heat treatment 2h, 260 DEG C of heat treatment 3h, obtain modified carrier DS5.
Table 3 embodiment and comparative example carrying alumina volume property
| Aluminium oxide is numbered | Z | S1 | S2 | S3 | S4 | S5 | S6 |
| Introduce B2O3, % | - | 1.5 | 1.5 | 1.0 | 2.0 | 1.0 | 5.5 |
| Introduce SiO2, % | - | 0.8 | 0.8 | 1.4 | 1.4 | 0.5 | 2.5 |
| Specific surface area, m2/g | 293 | 289 | 287 | 283 | 280 | 290 | 277 |
| Pore volume, mL/g | 0.66 | 0.65 | 0.64 | 0.63 | 0.63 | 0.65 | 0.61 |
| Infrared total acid, mmol/g | 0.409 | 0.515 | 0.499 | 0.512 | 0.532 | 0.506 | 0.500 |
Continued 3
| Aluminium oxide is numbered | DS1 | DS2 | DS3 | DS4 | DS5 |
| Introduce B2O3Amount, wt% | 2.0 | - | 1.5 | 1.5 | 1.0 |
| Introduce SiO2Amount, wt% | 1.4 | 0.8 | - | 0.8 | 12.0 |
| Specific surface area, m2/g | 302 | 295 | 292 | 290 | 242 |
| Pore volume, mL/g | 0.65 | 0.66 | 0.66 | 0.64 | 0.53 |
| Infrared total acid, mmol/g | 0.461 | 0.439 | 0.430 | 0.459 | 0.405 |
Embodiment 6 ~ 11
Take the carrier strip S1 in the embodiment of the present invention, S2, S3, S4, S5 and S6 respectively, after Mo, Ni, P solution respectively incipient impregnation 2h, 120 DEG C of dry 3h, 450 DEG C of roasting 2h, respectively obtain hydrotreating catalyst T1, T2, T3, T4, T5 and T6.
Comparative example 6 ~ 10
Take the carrier strip DS1 of comparative example of the present invention, DS2, DS3, DS4 and DS5 respectively, after Mo, Ni, P solution respectively incipient impregnation 2h, 120 DEG C of dry 3h, 450 DEG C of roasting 2h, respectively obtain hydrotreating catalyst DT1, DT2, DT3, DT4 and DT5.
Comparative example 11
With the impregnation liquid incipient impregnation carrier Z containing Mo, Ni, P, after 120 DEG C of dry 3h, 450 DEG C of roasting 2h, it is thus achieved that hydrotreating catalyst be designated as DT6.
The composition of table 4 catalyst
| Catalyst forms | T1 | T2 | T3 | T4 | T5 | T6 |
| MoO3, wt% | 20.22 | 20.19 | 20.39 | 20.31 | 20.29 | 20.35 |
| NiO, wt% | 3.95 | 4.05 | 4.01 | 4.10 | 4.12 | 4.03 |
| P, wt% | 1.35 | 1.36 | 1.33 | 1.34 | 1.31 | 1.33 |
Continued 4
| Catalyst forms | DT1 | DT2 | DT3 | DT4 | DT5 | DT6 |
| MoO3, wt% | 20.31 | 20.16 | 20.33 | 20.28 | 20.25 | 20.25 |
| NiO, wt% | 4.08 | 4.16 | 4.09 | 4.10 | 4.03 | 4.09 |
| P, wt% | 1.33 | 1.35 | 1.36 | 1.32 | 1.37 | 1.33 |
Adopting identical raw oil, embodiment and comparative example catalyst, in Table 5, are carried out active appraisal experiment by character under identical process conditions, and evaluating catalyst condition is reaction stagnation pressure 9.0MPa, volume space velocity 1.0h during liquid-1, hydrogen to oil volume ratio 800:1, reaction temperature is 380 DEG C.Result is in Table 6.
Table 5 raw material oil properties
| Raw oil | |
| Density (20 DEG C), g/cm3 | 0.9086 |
| Sulfur content, wt% | 2.26 |
| Nitrogen content, μ g/g | 1437 |
| Boiling range, DEG C | |
| IBP/ EBP | 301/535 |
Table 6 catalyst activity evaluation result
| Catalyst | T1 | T2 | T3 | T4 | T5 | T6 |
| Relative denitrification activity, % | 139 | 138 | 133 | 134 | 139 | 126 |
| Relatively desulphurizing activated, % | 126 | 126 | 124 | 124 | 126 | 120 |
Continued 6
| Catalyst | DT1 | DT2 | DT3 | DT4 | DT5 | DT6 |
| Relative denitrification activity, % | 105 | 107 | 103 | 108 | 102 | 100 |
| Relatively desulphurizing activated, % | 103 | 105 | 101 | 106 | 101 | 100 |
From table 6, compared with comparative example catalyst, the hydrotreating catalyst prepared with carrier of the present invention, hydrodesulfurization and denitrification activity all improve a lot, especially the activity of hydrodenitrogeneration.
Claims (18)
1. a preparation method for the siliceous alumina-based supports with boron, including: water-soluble silicon oil and solubility boron-containing compound are sequentially or simultaneously introduced alumina-based supports, after Overheating Treatment, prepares siliceous and boron alumina-based supports.
2. in accordance with the method for claim 1, it is characterized in that: introduced the silicone content in carrier by water-soluble silicon oil and account for the 0.1%～5.0% of modified oxidized alumina-based support weight in silicon dioxide, solubility boron-containing compound introduce the Boron contents in carrier and account for the 0.1%～10.0% of modified oxidized alumina-based support weight in boron oxide.
3. in accordance with the method for claim 1, it is characterized in that: introduced the silicone content in carrier by water-soluble silicon oil and account for the 0.2%～3.0% of modified oxidized alumina-based support weight in silicon dioxide, solubility boron-containing compound introduce the Boron contents in carrier and account for the 0.3%～6.0% of modified oxidized alumina-based support weight in boron oxide.
4. in accordance with the method for claim 1, it is characterized in that: introduced the silicone content in carrier by water-soluble silicon oil and account for the 0.2% ~ 0.9% of modified oxidized alumina-based support weight in silicon dioxide, solubility boron-containing compound introduce the Boron contents in carrier and account for the 0.5%～3.0% of modified oxidized alumina-based support weight in boron oxide.
5. according to the arbitrary described method of claim 1 ~ 4, it is characterised in that: introduce mol ratio that the consumption of water-soluble silicon oil and solubility boron-containing compound counts with silicon oxide and boron oxide respectively for 0.02 ~ 40.0, it is preferred to 0.04 ~ 10.0, more preferably 0.1 ~ 2.0.
6. in accordance with the method for claim 1, it is characterized in that: described water-soluble silicon oil properties is as follows: viscosity when 25 DEG C is 200 ~ 7000mPa.s, cloud point is 30 ~ 100 DEG C, it is preferable that as follows: viscosity when 25 DEG C is 500 ~ 5000mPa.s, and cloud point is 40 ~ 65 DEG C.
7. the method described in claim 1 or 6, it is characterised in that: described water-soluble silicon oil is polyether modified silicon oil.
8. in accordance with the method for claim 1, it is characterized in that: described alumina-based supports is with aluminium oxide for key component, contain or without there being adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, and adjuvant component content in alumina-based supports is at below 30wt%.
9. in accordance with the method for claim 1, it is characterised in that: alumina-based supports used is that aluminium hydroxide obtains after high-temperature roasting, and the condition of high-temperature roasting is as follows: at 450 DEG C～1000 DEG C roasting 1.0h～20.0h, it is preferred to 3.0h ~ 8.0h.
10. according to the arbitrary described method of claim 1 ~ 9, it is characterised in that: the character of described alumina-based supports is as follows: specific surface area is 120 ~ 420m2/ g, pore volume is 0.4 ~ 1.3mL/g, and bore dia accounts for less than the 20% of total pore volume less than the pore volume shared by the hole of 4nm.
11. in accordance with the method for claim 1, it is characterised in that: described solubility boron-containing compound is one or more in boric acid, ammonium pentaborate, tetraboric acid ammonium.
12. in accordance with the method for claim 1, it is characterized in that: described heat treatment adopts two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, the process time is 0.5h～20.0h, and second segment is 180 DEG C～400 DEG C in temperature, and the process time is 0.5h～20.0h, it is preferably as follows: first paragraph is 90 DEG C～120 DEG C in temperature, the process time is 1.0h～6.0h, and second segment is 200 DEG C～350 DEG C in temperature, and the process time is 1.0h～6.0h.
13. in accordance with the method for claim 1, it is characterized in that: water-soluble silicon oil and solubility boron-containing compound are sequentially introduced on carrier, its incorporation way adopts infusion process, namely first water-soluble silicon oil is impregnated on carrier, after health preserving, by Low Temperature Heat Treatment, then again solubility boron-containing compound is impregnated on carrier, by two sections of heat treatments, obtain modified oxidized alumina-based support；Wherein Low Temperature Heat Treatment is that the process time is 0.5h～20.0h at 60 DEG C～150 DEG C；In described two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, and the process time is 0.5h～20.0h, and second segment is 180 DEG C～400 DEG C in temperature, and the process time is 0.5h～20.0h.
14. in accordance with the method for claim 13, it is characterised in that: in the dipping solution be made into solubility boron-containing compound, boron-containing compound concentration is calculated as 0.1g/100mL ~ 20g/100mL with boron oxide；In the dipping solution being made into by water-soluble silicon oil, water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/100mL with silicon oxide.
15. in accordance with the method for claim 1, it is characterized in that: water-soluble silicon oil and solubility boron-containing compound are simultaneously introduced on carrier, its incorporation way adopts infusion process, it is impregnated on carrier by water-soluble silicon oil and solubility boron-containing compound simultaneously, after health preserving, by two sections of heat treatments, obtain modified oxidized alumina-based support.
16. in accordance with the method for claim 15, it is characterized in that: by the dipping solution of solubility boron-containing compound and water-soluble silicon oil mixed preparing, boron-containing compound concentration is calculated as 0.1g/100mL ~ 10g/100mL with boron oxide, and water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 10g/100mL with silicon oxide.
17. according to the arbitrary described method of claim 13 ~ 16, it is characterised in that: two sections of described heat treatments, first paragraph is 90 DEG C～120 DEG C in temperature, and the process time is 1.0h～6.0h, and second segment is 200 DEG C～350 DEG C in temperature, and the process time is 1.0h～6.0h.
18. according to the arbitrary described method of claim 13 ~ 16, it is characterised in that: infusion process adopts an incipient impregnation.
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