CN106669795A - Preparation method of hydro-upgrading catalyst - Google Patents
Preparation method of hydro-upgrading catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a hydro-upgrading catalyst. The method comprises the following steps: preparing a modified hydro-upgrading catalyst carrier, loading a hydrogenation active metal component by an impregnation method, drying and roasting to obtain a hydro-upgrading catalyst. The preparation of the modified hydro-upgrading catalyst carrier comprises the following steps: successively or simultaneously introducing water-soluble silicone oil and a soluble zirconium-containing compound into a hydro-upgrading catalyst carrier, and carrying out heat treatment to prepare the modified hydro-upgrading catalyst carrier. By the method, distribution of acid center and hydrogenation center can be adjusted for mutual coordination to enhance comprehensive properties of the catalyst. The catalyst is especially suitable to be used as a diesel hydro-upgrading catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for hydro-upgrading, particularly for the preparation method of diesel oil hydrogenation modification catalyst.
Background technology
For cleaning diesel production, prior art mainly includes the technology such as hydrofinishing and MHUG.Hydrofinishing can reduce modifying the sulfur content of diesel oil, but limited to improving Cetane number and reduction T95 temperature capabilities.MHUG is using containing molecular sieve（Such as Y type molecular sieve, beta-molecular sieve）Catalyst for hydro-upgrading, aromatic hydrocarbons in diesel oil etc. is suitably cracked, while sulphur, nitrogen impurity content in reducing diesel oil, improve the combination properties such as diesel cetane-number.But using current catalyst for hydro-upgrading, the combination property to improve diesel oil（Sulphur nitrogen impurity content, Cetane number, T95 temperature, arene content etc.）, it usually needs higher cracking degree, can so make diesel yield relatively low, and the yield of diesel oil is kept, the combination property of diesel oil is again less than improvement well.
Sulfur-containing compound and aromatic hydrocarbons in diesel oil distillate, generally exist with complicated structure, such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene etc., wherein be hydrogenated with more difficult removing is the thiophenes such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene, especially with 4,6-
Dimethyl Dibenzothiophene（4,6- BMDBT）With
2,4,6- trimethyl dibenzothiophenes（2,4,6- BMDBT）Class formation is complicated and sulfur-containing compound that have space steric effect is most difficult to removing.Reach depth and ultra-deep desulfurization, it is accomplished by removing these complex structures and sterically hindered big sulfur-containing compound, and the generally more difficult removing under the harsh hydrofinishing operating condition such as HTHP of these sulfur-containing compounds, by being hydrocracked, diesel yield can be reduced.Therefore, in the case where keeping diesel yield higher, the impurity in diesel oil how is removed, while and the combination property of diesel oil can be improved, this is the important topic for being currently needed for studying.
Catalyst for hydro-upgrading is typically with the alumina support containing molecular sieve, at present, the method being modified to carrier 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 property of carrier, but because the consumption, the species that introduce auxiliary agent are different with mode, the property of alumina support can be made different, or even difference is very big.CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, and the catalyst consists of 40～80wt% of aluminum oxide, 0～20wt% of amorphous silica-alumina, 5～30wt% of Y type molecular sieve.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly the predecessor using silica-alumina, aluminum oxide and/or aluminum oxide and Y type molecular sieve mixing, shaping and roasting, introduce afterwards the hydrogenation metal of effective dose in shaping species.Above-mentioned catalyst has higher desulfurization and a denitrification activity, but the amplitude that the yield of diesel product is low, diesel oil Cetane number is improved is little, high condensation point and the shortcomings of big density.
CN201110350790.2 discloses a kind of diesel oil hydrogenation modification catalyst and preparation method thereof.The catalyst includes the carrier and hydrogenation active metals component being made up of modified beta molecular sieve and aluminum oxide.When being used for diesel oil hydrogenation modification using the catalyst, although the condensation point of diesel oil distillate can be reduced, the Cetane number of modification diesel oil is improved, but diesel yield is below 97%, it is still relatively low.
The content of the invention
For problems of the prior art, the invention provides a kind of preparation method of catalyst for hydro-upgrading.The catalyst passes through support modification, carrier is set to provide more B acid sites, reduce strong acid center, and can adjust the distribution of acid centre and hydrogenation sites, make its mutually coordinated effect, the combination property of catalyst is improved, the catalyst for hydro-upgrading is adapted to the upgrading processes of various distillates, be especially suitable for the hydro-upgrading of diesel oil distillate.
The preparation method of the catalyst for hydro-upgrading that the present invention is provided, including the preparation of modified catalyst for hydro-upgrading carrier, using infusion process hydrogenation active metals component is loaded, drying and roasting, hydrotreating catalyst is obtained, wherein the preparation method of modified catalyst for hydro-upgrading carrier, including：Water-soluble silicon oil and soluble zirconium-containing compound are sequentially or simultaneously introduced into catalyst for hydro-upgrading carrier, after heat treatment, modified catalyst for hydro-upgrading carrier is obtained.
Catalyst for hydro-upgrading carrier of the present invention, it can be the catalyst for hydro-upgrading carrier of conventional method preparation, usually with aluminum oxide and molecular sieve as key component, adjuvant component can not contained, adjuvant component can also be contained, wherein adjuvant component can be one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component content in the carrier in below 15wt%, preferred below 10wt%.Catalyst for hydro-upgrading carrier of the present invention can be prepared using kneading method, mixing plastic method etc., and the general process of kneading method is as follows, by aluminium hydroxide（Such as boehmite）With obtain after high-temperature roasting after molecular sieve mixed-forming, the condition of high-temperature roasting is as follows：In 450 DEG C～1000 DEG C roasting 1.0h～20.0h, preferably 3.0 h ~ 8.0 h.The general process of mixing plastic method is that molecular sieve is introduced during alumine hydroxide colloid is prepared, and after plastic, the alumina dry glue containing molecular sieve is obtained, and Jing shapings are dried and roasting, make carrier.The shape of carrier can as needed make spherical, bar shaped（Such as clover, bunge bedstraw herb or cylindrical bars）Etc. suitable shape, conventional shaping assistant, such as the acid of extrusion aid, peptization, adhesive etc. can be added in forming process.The property of the catalyst for hydro-upgrading carrier is as follows：Specific surface area is 200 ~ 550m2/ g, preferably 280 ~ 450m2/g；Pore volume is 0.4 ~ 1.3mL/g, preferably 0.6 ~ 1.0mL/g.
Molecular sieve of the present invention is Y type molecular sieve and/or beta-molecular sieve.On the basis of the weight of catalyst for hydro-upgrading carrier, the content of molecular sieve is 3% ~ 35%, and the content of aluminum oxide is 65% ~ 97%, and preferably the content of molecular sieve is 3% ~ 20%, and the content of aluminum oxide is 80% ~ 97%.Wherein described molecular sieve is hydrogen type molecular sieve.Wherein beta-molecular sieve preferred property is as follows：SiO2/Al2O3Mol ratio is 30 ~ 150, specific surface area 400m2/ g～750m2/ g, total pore volume 0.30mL/g～0.55mL/g, meleic acid 0.1～0.8mmol/g of amount；Y type molecular sieve preferred property is as follows：SiO2/Al2O3Mol ratio is 5 ~ 50, specific surface area 450m2/ g～800m2/ g, total pore volume 0.30mL/g～0.60mL/g, meleic acid 0.2～0.9mmol/g of amount.Beta-molecular sieve of the present invention and Y type molecular sieve can be prepared using existing method.
In the inventive method, the silicone content being introduced into carrier by water-soluble silicon oil accounts for the 0.2%～7.0% of modified catalyst for hydro-upgrading vehicle weight in terms of silica, and preferably 0.3%～4.0%, more preferably 0.5% ~ 1.8%.
In the inventive method, the zirconium content being introduced into carrier by soluble zirconium-containing compound accounts for the 0.4%～10.0% of modified catalyst for hydro-upgrading vehicle weight in terms of zirconium oxide, and preferably 0.5%～5.0%, more preferably 0.5%～2.5%.
In the inventive method, mol ratio that the consumption of water-soluble silicon oil and soluble zirconium-containing compound counted with silica and zirconium oxide respectively is introduced as 0.04 ~ 36.0, preferably 0.12 ~ 16.0, more preferably 0.40 ~ 7.5.
Water-soluble silicon oil described in the inventive method, referring to can be dissolved in the silicone oil of water, and preferred property is as follows：Viscosity when 25 DEG C is 200 ~ 7000mPa.s, and preferably 500 ~ 5000mPa.s, cloud point is 30 ~ 100 DEG C, preferably 40 ~ 65 DEG C.What described water-soluble silicon oil was usually obtained using the method for group modified silicone oil, such as polyether modified silicon oil.
In the inventive method, soluble zirconium-containing compound refers to the combination of one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride etc..
In the inventive method, water-soluble silicon oil and soluble zirconium-containing compound are sequentially or simultaneously incorporated on catalyst for hydro-upgrading carrier, first water-soluble silicon oil can be incorporated on catalyst for hydro-upgrading carrier, then soluble zirconium-containing compound is incorporated on catalyst for hydro-upgrading carrier again；Or simultaneously water-soluble silicon oil and soluble zirconium-containing compound are incorporated on catalyst for hydro-upgrading carrier, its incorporation way adopts infusion process, and infusion process can be incipient impregnation, or excessive dipping；Can be repeatedly dipping, or single-steeping.To improve efficiency, preferably using an incipient impregnation.
In the inventive method, described heat treatment is using two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, preferably 90 DEG C～120 DEG C, process time is 0.5h～20.0h, preferably 1.0h～6.0h, second segment is 180 DEG C～400 DEG C in temperature, preferably 200 DEG C～350 DEG C, process time is 0.5h～20.0h, preferably 1.0h～6.0h.Heat treatment can be carried out in oxygen-containing atmosphere, oxygen concentration is not particularly limited, such as air atmosphere, it is also possible to carry out in an inert atmosphere, such as nitrogen atmosphere etc..
In the inventive method, described hydrogenation active metals component is the active metal component that catalyst for hydro-upgrading is commonly used, one or more generally in vib metals and group VIII metal, wherein vib metals are preferably W and/or Mo, and group VIII metal is preferably Co and/or Ni.
Catalyst for hydro-upgrading prepared by the inventive method, on the basis of the weight of catalyst, the content of modified catalyst for hydro-upgrading carrier is 55.0wt% ~ 94.5wt%, preferably 58.0wt% ~ 90.0wt%, vib metals oxide content is 5.0wt% ~ 30.0wt%, preferably 8.0wt% ~ 30.0wt%, group VIII metal oxide content is 0.5wt% ~ 15.0 wt%, preferably 2.0 wt % ~ 12.0 wt
%。
In catalyst for hydro-upgrading preparation method of the present invention, hydrogenation active metals component is supported on carrier by infusion process, can be incipient impregnation, or excessive dipping, can be step impregnation, may also be co-impregnation, preferably equal-volume co-impregnation.Dipping method is well-known to those skilled in the art.After hydrogenation active metals component solution impregnated carrier, final catalyst is made in drying and roasting.Method for preparing catalyst is known to technical staff.By being prepared with the compound containing group VIB or group VIII metal, its solution concentration can be adjusted dipping solution by the consumption of each compound, and so as to prepare the catalyst of specified activity constituent content, the compound method of solution is known to those skilled in the art.With the aqueous impregnation said catalyst carrier containing active metal component, through dry and calcination stepses after dipping.The condition of the drying and roasting is conventional, and for example, baking temperature is 60 DEG C～200 DEG C, and preferably 90 DEG C～160 DEG C, drying time is 0.5h～20h, preferably 1h～6h；Sintering temperature is 300 DEG C～700 DEG C, and preferably 300 DEG C～500 DEG C, roasting time is 0.5h～20h, preferably 1h～6h.
Modified catalyst for hydro-upgrading carrier prepared by the inventive method, with a small amount of specific water-soluble silicon oil-impregnated catalyst for hydro-upgrading carrier, it is set to load on the ad-hoc location of catalyst for hydro-upgrading carrier surface using the effect of the hydrophilic and hydrophobic grouping of water-soluble silicon oil, and the zirconium-containing compound for impregnating simultaneously or afterwards is evenly spread to around silica group, by suitable heat treatment, the Si for being loaded, the more preferable coordinative role of Zr energy, the silicon zirconium hydroxyl being more evenly distributed is formed in carrier surface ad-hoc location, on the one hand carrier surface is made to form more acid suitable acid centres, and be engaged with the former acidic site in carrier, make the acidity and acid distribution of carrier more reasonable, reduce strong acid content, more B acid sites are provided, on the other hand, be conducive to adjusting the distribution of the hydrogenation sites that the follow-up active metal using infusion process load is formed, and the cooperation of the acid centre of hydrogenation sites and carrier, so as to improve the performance of catalyst.
Catalyst prepared by the inventive method, the suitable catalyst for hydro-upgrading as various distillates, particularly diesel oil hydrogenation modification catalyst, the catalyst is used for during diesel oil hydrogenation modification, with deep hydrodesulfurizationof activity, and can keep improving the combination properties such as Cetane number in the case that diesel yield is higher.
Specific embodiment
In the present invention, cloud point refers to that the water-soluble silicon oil solution that mass concentration is 1% is heated to after muddiness and stops heating, temperature of the lower observation aqueous solution of stirring by muddy change when limpid.
The preparation method of the modified catalyst for hydro-upgrading carrier provided according to the present invention, it can specifically adopt following steps：
1st, soluble zirconium-containing compound is configured into solution A, wherein zirconium-containing compound concentration is calculated as 0.1g/100mL ~ 32g/100mL with zirconium oxide；
2nd, water-soluble silicon oil is configured into solution B, wherein water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/100mL with silica；
3rd, soluble zirconium-containing compound and water-soluble silicon oil are hybridly prepared into solution C, wherein zirconium-containing compound concentration is calculated as 0.1g/100mL ~ 16g/100mL with zirconium oxide, and water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 10g/100mL with silica；
4th, water-soluble silicon oil and zirconium-containing compound are guided on catalyst for hydro-upgrading carrier using a kind of at least following mode：
I, impregnate catalyst for hydro-upgrading carrier with solution C, preferably through health after, then by two sections of heat treatments, obtain modified catalyst for hydro-upgrading carrier；In wherein two sections heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, preferably 90 DEG C～120 DEG C, process time is 0.5h～20.0h, preferably 1.0h～6.0h, second segment is 180 DEG C～400 DEG C, preferably 200 DEG C～350 DEG C in temperature, process time is 0.5h～20.0h, preferably 1.0h～6.0h；
II, impregnate catalyst for hydro-upgrading carrier with solution B, preferably through health after, by Low Temperature Heat Treatment, then dipping solution A, preferably through health after, then by two sections of heat treatments, obtain modified catalyst for hydro-upgrading carrier；Wherein Low Temperature Heat Treatment is that process time is 0.5h～20.0h, preferably 1.0h～6.0h at 60 DEG C～150 DEG C, preferably 90 DEG C～120 DEG C；In two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, preferably 90 DEG C～120 DEG C, process time is 0.5h～20.0h, preferably 1.0h～6.0h, second segment is 180 DEG C～400 DEG C, preferably 200 DEG C～350 DEG C in temperature, process time is 0.5h～20.0h, preferably 1.0h～6.0h.
In the inventive method, heat treatment can be carried out in oxygen-containing atmosphere, oxygen concentration is not particularly limited, such as air atmosphere, it is also possible to be carried out in an inert atmosphere, such as nitrogen atmosphere etc..
The inventive method is not specifically limited to the conditioned time after dipping solution, conditioned time is defined by can guarantee that water-soluble silicon oil and the uniform adsorption of zirconium-containing compound component, those skilled in the art can be judged to determine conditioned time according to the absorption situation of the viscosity situation of solution and solution.
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, meleic acid amount, B acid and L acid are determined using Pyridine adsorption IR spectra method, and wherein meleic acid amount is the sum of B acid and L acid acid amounts.
In embodiment, water-soluble silicon oil A used is by the industrial organosilicon new material company production in Qingdao, SiO2Content is 15wt%, viscosity（25℃）1500 ~ 5000 mPa.s, cloud point is 47 DEG C；Water-soluble silicon oil B is produced by Laiyang is along bright Chemical Co., Ltd, SiO2Content is 9wt%, viscosity（25℃）For 500～1500mPa.s, cloud point is 45～55 DEG C；Water-soluble silicon oil C is produced by Laiyang Sheng Bang organosilicons Science and Technology Ltd.,SiO2Content is 30wt%, viscosity（25℃）For 600～5000mPa.s, cloud point is 42～46 DEG C.
In embodiment, the property of beta-molecular sieve B1 used is as follows：SiO2/Al2O3Mol ratio is 40, specific surface area 530m2/ g, total pore volume 0.45mL/g, meleic acid amount 0.44mmol/g；The property of beta-molecular sieve B2 used is as follows：SiO2/Al2O3Mol ratio is 70, specific surface area 548m2/ g, total pore volume 0.46mL/g, meleic acid amount 0.39mmol/g.The property of Y type molecular sieve Y1 used is as follows：SiO2/Al2O3Mol ratio is 12, specific surface area 628m2/ g, total pore volume 0.48mL/g, meleic acid amount 0.49mmol/g；The property of Y type molecular sieve Y2 used is as follows：SiO2/Al2O3Mol ratio is 25, specific surface area 640m2/ g, total pore volume 0.49mL/g, meleic acid amount 0.45mmol/g.
The diameter of cylindrical vector used is about 1.2mm in embodiment, and length is about 3 ~ 5mm, and its physico-chemical property is as shown in table 1.
The preparation of Z1：By beta-molecular sieve B1, macroporous aluminium oxide (pore volume 1.0mL/g, specific surface area 400m2/ g), adhesive (mol ratio of nitric acid and little porous aluminum oxide is 0.3) be put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar then in 550 DEG C of roastings 4 hours, obtains carrier Z1 in 110 DEG C of dryings 4 hours.
The preparation of Z2：By beta-molecular sieve B1, Y type molecular sieve Y1, macroporous aluminium oxide (pore volume 1.0mL/g, specific surface area 400m2/ g), adhesive (mol ratio of nitric acid and little porous aluminum oxide is 0.3) be put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar then in 550 DEG C of roastings 4 hours, obtains carrier Z2 in 110 DEG C of dryings 4 hours.
The preparation of Z3：By beta-molecular sieve B2, Y type molecular sieve Y2, macroporous aluminium oxide (pore volume 1.0mL/g, specific surface area 400m2/ g), adhesive (mol ratio of nitric acid and little porous aluminum oxide is 0.3) be put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar then in 550 DEG C of roastings 4 hours, obtains carrier Z3 in 110 DEG C of dryings 4 hours.
The physico-chemical property of catalyst for hydro-upgrading carrier used in the embodiment of table 1
| Project | Z1 | Z2 | Z3 |
| Beta-molecular sieve content, wt% | _ | 4 | 6 |
| Y molecular sieve content, wt% | 10 | 6 | 6 |
| Aluminum oxide | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 350 | 341 | 362 |
| Pore volume, mL/g | 0.63 | 0.64 | 0.64 |
| Saturation liquid absorption, mL/100g | 72 | 73 | 73 |
Mo predecessors in the present embodiment in Mo, Ni, P maceration extract used are MoO3, Ni predecessors are basic nickel carbonate, and P predecessors are phosphoric acid.
Embodiment 1
Zirconium nitrate 18.6g is weighed, appropriate amount of deionized water dissolving is added, makes volume be 105mL, obtained solution A1.Water-soluble silicon oil A 21.0g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 105mL, obtained solution B1.Under stirring, 35mL B1 solution is poured slowly into 35mL A1 solution, and adds appropriate amount of deionized water, make final volume be 72mL, be configured to C1 solution.
100g catalyst for hydro-upgrading carrier Z1 are taken, solution C 1 is uniformly sprayed on carrier Z1, after health 10 hours, 100 DEG C of heat treatment 2h of Jing, 230 DEG C of heat treatment 2h obtain modified carrier S 1.
Take 100g catalyst for hydro-upgrading carrier Z1, the deionized water of 35mL solution Bs 1 is diluted into 72mL, uniformly it is sprayed on carrier Z1, health 10 hours, Jing after 100 DEG C are heat-treated 2h, again 35mL A1 solution deionized waters are diluted into 71mL, uniformly it is sprayed on carrier Z1, after health 3 hours, 100 DEG C of heat treatment 2h of Jing, 230 DEG C of heat treatment 2h, obtain modified carrier S 2.
Embodiment 2
Zirconium oxychloride 13.0g, water-soluble silicon oil B 36.0g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 146mL, obtained solution C2.
100g catalyst for hydro-upgrading carrier Z1 are taken, 73mL solution Cs 2 are uniformly sprayed on carrier Z1, after health 10 hours, 100 DEG C of heat treatment 2h of Jing, 230 DEG C of heat treatment 2h obtain modified carrier S 3.
100g catalyst for hydro-upgrading carrier Z1 are taken, 73mL solution Cs 2 are uniformly sprayed on carrier Z1, after health 10 hours, in a nitrogen atmosphere, 100 DEG C of heat treatment 2h of Jing, 350 DEG C of heat treatment 2h obtain modified carrier S 4.
Embodiment 3
Zirconium nitrate 3.6g, water-soluble silicon oil C2.7g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 73mL, obtained solution C3.
100g catalyst for hydro-upgrading carrier Z2 are taken, solution C 3 is uniformly sprayed on carrier Z2, after health 10 hours, 100 DEG C of heat treatment 2h of Jing, 260 DEG C of heat treatment 2h obtain modified carrier S 5.
Embodiment 4
Zirconium nitrate 16.5g, the g of water-soluble silicon oil C 12.5 are weighed, appropriate amount of deionized water dissolving is added, makes volume be 73mL, obtained solution C4.
100g catalyst for hydro-upgrading carrier Z2 are taken, solution C 4 is uniformly sprayed on carrier Z2, after health 10 hours, 100 DEG C of heat treatment 2h of Jing, 260 DEG C of heat treatment 2h obtain modified carrier S 6.
Embodiment 5
Zirconium nitrate 7.2g, water-soluble silicon oil C 2.7g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 73mL, obtained solution C5.
100g catalyst for hydro-upgrading carrier Z3 are taken, solution C 3 is uniformly sprayed on catalyst for hydro-upgrading carrier Z3, after health 10 hours, 100 DEG C of heat treatment 2h of Jing, 260 DEG C of heat treatment 2h obtain modified carrier S 7.
Comparative example 1
Water-soluble silicon oil A 7.0g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 72mL, obtained solution B2.100g catalyst for hydro-upgrading carrier Z1 are taken, solution B 2 is uniformly sprayed on carrier Z1, after health 10 hours, 100 DEG C of heat treatment 2h of Jing, 230 DEG C of heat treatment 2h obtain modified carrier DS1.
Comparative example 2
Zirconium nitrate 6.2g is weighed, appropriate amount of deionized water dissolving is added, makes volume be 72mL, be configured to A2 solution.100g catalyst for hydro-upgrading carrier Z1 are taken, solution A 2 is uniformly sprayed on carrier Z1, after health 10 hours, 100 DEG C of heat treatment 2h of Jing, 230 DEG C of heat treatment 2h obtain modified carrier DS2.
Comparative example 3
Compared with the preparation method of carrier S 2 in embodiment 2, this comparative example is first to introduce zirconates, and water-soluble silicon oil is introduced afterwards, and detailed process is as follows：
Take 100g catalyst for hydro-upgrading carrier Z1,35mL A1 solution deionized waters are diluted into 72mL, uniformly it is sprayed on carrier Z1, after health 3 hours, 100 DEG C of heat treatment 2h of Jing, again the deionized water of 35mL solution Bs 1 is diluted into 71mL, uniformly it is sprayed on carrier Z1, health 10 hours, Jing after 100 DEG C are heat-treated 2h, 230 DEG C of heat treatment 2h, obtain modified carrier DS3.
Table 2
Embodiment and the catalyst for hydro-upgrading support prepared by comparative example
| Bearer number | S1 | S2 | S3 | S4 | S5 | S6 | S7 |
| Introduce ZrO2Amount, wt% | 1.7 | 1.7 | 2.3 | 2.3 | 1.0 | 4.4 | 2.0 |
| Introduce SiO2Amount, wt% | 1.0 | 1.0 | 1.5 | 1.5 | 0.8 | 3.5 | 0.8 |
| Specific surface area, m2/g | 304 | 302 | 295 | 2922 | 312 | 279 | 311 |
| Pore volume, mL/g | 0.61 | 0.61 | 0.60 | 0.60 | 0.62 | 0.57 | 0.62 |
| Infrared total acid, mmol/g | 0.528 | 0.507 | 0.522 | 0.535 | 0.508 | 0.482 | 0.512 |
| B is sour, mmol/g | 0.122 | 0.119 | 0.125 | 0.131 | 0.118 | 0.110 | 0.119 |
| L is sour, mmol/g | 0.406 | 0.388 | 0.397 | 0.404 | 0.390 | 0.372 | 0.393 |
| Strong acid content *, % | 15.3 | 14.8 | 14.5 | 14.9 | 15.1 | 13.9 | 14.8 |
* note：In table 2, strong acid content refers to that acid amount when measuring using determination of infrared spectroscopy acid more than 450 DEG C accounts for the percentage of total acid content.
Continued 2
| Bearer number | Z1 | Z2 | Z3 | DS1 | DS2 | DS3 |
| Introduce ZrO2Amount, wt% | - | - | - | - | 1.7 | 1.7 |
| Introduce SiO2Amount, wt% | - | - | - | 1.0 | - | 1.0 |
| Specific surface area, m2/g | 350 | 341 | 362 | 321 | 323 | 303 |
| Pore volume, mL/g | 0.63 | 0.64 | 0.64 | 0.62 | 0.62 | 0.61 |
| Infrared total acid, mmol/g | 0.445 | 0.457 | 0.440 | 0.467 | 0.429 | 0.448 |
| B is sour, mmol/g | 0.075 | 0.078 | 0.076 | 0.080 | 0.061 | 0.071 |
| L is sour, mmol/g | 0.370 | 0.379 | 0.364 | 0.387 | 0.368 | 0.377 |
| Strong acid content *, % | 24.7 | 23.9 | 24.5 | 20.8 | 12.5 | 13.5 |
Embodiment 6 ~ 12
Carrier strip S1, S2, S3, S4, S5, S6 and the S7 in the embodiment of the present invention being taken respectively, being distinguished after incipient impregnation 2h with Mo, Ni, P solution, 120 DEG C are dried 3h, 480 DEG C of roasting 2h, respectively obtain catalyst T1, T2, T3, T4, T5, T6 and T7.
Comparative example 4 ~ 8
Carrier strip DS1, DS2 and DS3 of comparative example of the present invention are taken respectively, and carrier Z1 and Z2 used in embodiment, with Mo, Ni, P solution difference incipient impregnation 2h after, 120 DEG C are dried 3h, 480 DEG C of roasting 2h, respectively obtain catalyst DT1, DT2, DT3, DT4 and DT5.
The composition of the catalyst of table 3
| Catalyst is constituted | T1 | T2 | T3 | T4 | T5 | T6 | T7 |
| MoO3, wt% | 23.52 | 23.54 | 23.71 | 23.80 | 23.75 | 23.81 | 23.73 |
| NiO, wt% | 3.97 | 4.11 | 3.98 | 3.96 | 4.08 | 4.06 | 4.05 |
| P, wt% | 1.25 | 1.26 | 1.22 | 1.23 | 1.25 | 1.23 | 1.24 |
Continued 3
| Catalyst is constituted | DT1 | DT2 | DT3 | DT4 | DT5 |
| MoO3, wt% | 23.85 | 23.77 | 23.81 | 23.79 | 23.88 |
| NiO, wt% | 3.99 | 3.95 | 4.07 | 4.09 | 3.98 |
| P, wt% | 1.23 | 1.25 | 1.22 | 1.24 | 1.23 |
Embodiment 13
The present embodiment is the henchnmrk test of catalyst.
Catalyst performance evaluation experiment is carried out on 100mL small hydrogenation devices, and presulfurization is carried out to catalyst before performance evaluation.Evaluating catalyst condition is in reaction stagnation pressure 10.0MPa, the h of volume space velocity 1.5 during liquid-1, hydrogen to oil volume ratio 800：1, reaction temperature is 365 DEG C.Henchnmrk test raw material oil nature is shown in Table 4, Evaluation results are shown in Table 5, from data in table, catalyst for hydro-upgrading is prepared with the present invention, catalyst it is desulphurizing activated apparently higher than comparative example catalyst, the Cetane number of diesel oil is improved into more than 10 units under conditions of diesel yield is kept not less than 98%, product quality has obtained good improvement.
Table
4
Raw material oil nature
| Feedstock oil | Catalytic diesel oil |
| Density (20 DEG C), g/cm3 | 0.9579 |
| Boiling range/DEG C | |
| IBP/ EBP | 188/375 |
| Condensation point, DEG C | 5 |
| Total sulfur, μ g/g | 8785 |
| 4,6-BMDBT contents, μ g/g | 100.5 |
| Nitrogen, μ g/g | 1158 |
| Cetane number | 28.5 |
| C, wt% | 87.63 |
| H, wt% | 11.05 |
Table
5
Catalyst performance
Evaluation result
| Catalyst is numbered | T1 | T2 | T3 | T4 | T5 | T6 | T7 |
| Diesel oil | |||||||
| Yield, wt% | 98.5 | 98.5 | 98.3 | 98.4 | 98.6 | 98.6 | 98.5 |
| Density (20 DEG C), g/cm3 | 0.8403 | 0.8402 | 0.8405 | 0.8402 | 0.8403 | 0.8401 | 0.8401 |
| T95, DEG C | 350 | 351 | 351 | 349 | 349 | 350 | 350 |
| Condensation point, DEG C | -21 | -22 | -21 | -20 | -22 | -21 | -22 |
| Cetane number | 47.9 | 48.1 | 48.0 | 48.2 | 48.3 | 47.7 | 48.1 |
| Sulphur, μ g/g | 7 | 6 | 6 | 5 | 6 | 6 | 6 |
Continued 5
| Catalyst is numbered | DT1 | DT2 | DT3 | DT4 | DT5 |
| Diesel oil | |||||
| Yield, wt% | 97.5 | 97.6 | 97.3 | 97.1 | 97.1 |
| Density (20 DEG C), g/cm3 | 0.8396 | 0.8415 | 0.8401 | 0.8378 | 0.8382 |
| T95, DEG C | 346 | 352 | 347 | 345 | 345 |
| Condensation point, DEG C | -20 | -17 | -19 | -21 | -22 |
| Cetane number | 45.6 | 43.0 | 44.5 | 44.8 | 45.0 |
| Sulphur, μ g/g | 10 | 19 | 14 | 13 | 12 |
Claims (23)
1. a kind of preparation method of catalyst for hydro-upgrading, including：The preparation of modified catalyst for hydro-upgrading carrier, using infusion process hydrogenation active metals component, drying and roasting are loaded, and obtain catalyst for hydro-upgrading, wherein the preparation method of modified catalyst for hydro-upgrading carrier includes：Water-soluble silicon oil and soluble zirconium-containing compound are sequentially or simultaneously introduced into catalyst for hydro-upgrading carrier, after heat treatment, modified catalyst for hydro-upgrading carrier is obtained.
2. in accordance with the method for claim 1, it is characterised in that：Described catalyst for hydro-upgrading carrier, it is with aluminum oxide and molecular sieve as key component, with or without adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, and content of the adjuvant component in terms of element in the carrier is in below 15wt%.
3. in accordance with the method for claim 1, it is characterised in that：The property of the catalyst for hydro-upgrading carrier is as follows：Specific surface area is 200 ~ 550m2/ g, pore volume is 0.4 ~ 1.3mL/g；It is preferably as follows：Specific surface area is 280 ~ 450m2/ g, pore volume is 0.6 ~ 1.0mL/g.
4. in accordance with the method for claim 1, it is characterised in that：Described catalyst for hydro-upgrading carrier is prepared using kneading method or mixing plastic method.
5. according to the method described in claim 1 or 4, it is characterised in that：Described catalyst for hydro-upgrading carrier is that Jing is molded and through the catalyst for hydro-upgrading carrier of high-temperature roasting, and the condition of high-temperature roasting is as follows：In 450 DEG C～1000 DEG C roasting 1.0h～20.0h.
6. in accordance with the method for claim 1, it is characterised in that：On the basis of the weight of catalyst for hydro-upgrading carrier, the content of molecular sieve is 3% ~ 35%, and the content of aluminum oxide is 65% ~ 97%, and preferably the content of molecular sieve is 3% ~ 20%, and the content of aluminum oxide is 80% ~ 97%.
7. in accordance with the method for claim 1, it is characterised in that：Described molecular sieve is Y type molecular sieve and/or beta-molecular sieve.
8. in accordance with the method for claim 6, it is characterised in that：Described molecular sieve is hydrogen type molecular sieve, and wherein beta-molecular sieve property is as follows：SiO2/Al2O3Mol ratio is 30 ~ 150, specific surface area 400m2/ g～750m2/ g, total pore volume 0.30mL/g～0.55mL/g, meleic acid 0.1～0.8mmol/g of amount；Y type molecular sieve property is as follows：SiO2/Al2O3Mol ratio is 5 ~ 50, specific surface area 450m2/ g～800m2/ g, total pore volume 0.30mL/g～0.60mL/g, meleic acid 0.2～0.9mmol/g of amount.
9. in accordance with the method for claim 1, it is characterised in that：The silicone content being introduced into carrier by water-soluble silicon oil accounts for the 0.2%～7.0% of modified catalyst for hydro-upgrading vehicle weight in terms of silica, and preferably 0.3%～4.0%, more preferably 0.5% ~ 1.8%.
10. according to the method described in claim 1 or 9, it is characterised in that：The zirconium content being introduced into carrier by soluble zirconium-containing compound accounts for the 0.4%～10.0% of modified catalyst for hydro-upgrading vehicle weight in terms of zirconium oxide, and preferably 0.5%～5.0%, more preferably 0.5%～2.5%.
11. according to the method described in claim 1 or 9, it is characterised in that：Mol ratio that the consumption of water-soluble silicon oil and soluble zirconium-containing compound counted with silica and zirconium oxide respectively is introduced as 0.04 ~ 36.0, preferably 0.12 ~ 16.0, more preferably 0.40 ~ 7.5.
12. in accordance with the method for claim 1, it is characterised in that：The property of described water-soluble silicon oil is as follows：Viscosity when 25 DEG C is 200 ~ 7000mPa.s, and cloud point is 30 ~ 100 DEG C, is preferably as follows：Viscosity when 25 DEG C is 500 ~ 5000mPa.s, and cloud point is 40 ~ 65 DEG C.
13. according to the method described in claim 1 or 12, it is characterised in that：Described water-soluble silicon oil is polyether modified silicon oil.
14. in accordance with the method for claim 1, it is characterised in that：Described soluble zirconium-containing compound is one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride.
15. in accordance with the method for claim 1, it is characterised in that：Described heat treatment is 60 DEG C～150 DEG C in temperature using two sections of heat treatments, first paragraph, and process time is 0.5h～20.0h, and second segment is 180 DEG C～400 DEG C in temperature, and process time is 0.5h～20.0h, is preferably as follows：First paragraph is 90 DEG C～120 DEG C in temperature, and process time is 1.0h～6.0h, and second segment is 200 DEG C～350 DEG C in temperature, and process time is 1.0h～6.0h.
16. in accordance with the method for claim 1, it is characterised in that：Water-soluble silicon oil and soluble zirconium-containing compound are successively incorporated on carrier, its incorporation way adopts infusion process, first water-soluble silicon oil is impregnated on carrier, Jing after health, by Low Temperature Heat Treatment, then soluble zirconium-containing compound is impregnated on carrier again, by two sections of heat treatments, obtains modified catalyst for hydro-upgrading carrier；Wherein Low Temperature Heat Treatment is that process time is 0.5h～20.0h at 60 DEG C～150 DEG C.
17. in accordance with the method for claim 16, it is characterised in that：In the dipping solution that soluble zirconium-containing compound is made into, zirconium-containing compound concentration is calculated as 0.1g/100mL ~ 32g/100mL with zirconium oxide；In the dipping solution that water-soluble silicon oil is made into, water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/100mL with silica.
18. in accordance with the method for claim 1, it is characterised in that：Water-soluble silicon oil and soluble zirconium-containing compound are incorporated on carrier simultaneously, its incorporation way adopts infusion process, will water-soluble silicon oil and soluble zirconium-containing compound be impregnated on carrier simultaneously, Jing after health, by two sections of heat treatments, modified catalyst for hydro-upgrading carrier is obtained.
19. in accordance with the method for claim 18, it is characterised in that：By in the dipping solution of soluble zirconium-containing compound and water-soluble silicon oil mixed preparing, zirconium-containing compound concentration is calculated as 0.1g/100mL ~ 16g/100mL with zirconium oxide, and water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 10g/100mL with silica.
20. according to the arbitrary described method of claim 16 ~ 19, it is characterised in that：Infusion process adopts an incipient impregnation.
21. according to the arbitrary described method of claim 16 ~ 19, it is characterised in that：Two sections of described heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, and process time is 0.5h～20.0h, and second segment is 180 DEG C～400 DEG C in temperature, and process time is 0.5h～20.0h, is preferably as follows：First paragraph is 90 DEG C～120 DEG C in temperature, and process time is 1.0h～6.0h, and second segment is 200 DEG C～350 DEG C in temperature, and process time is 1.0h～6.0h.
22. in accordance with the method for claim 1, it is characterised in that：Described hydrogenation active metals component is one or more in vib metals and group VIII metal, and wherein vib metals are W and/or Mo, and group VIII metal is Co and/or Ni.
23. in accordance with the method for claim 22, it is characterised in that：On the basis of the weight of catalyst, the content of modified catalyst for hydro-upgrading carrier is 55.0wt% ~ 94.5wt%, preferably 58.0wt% ~ 90.0wt%, vib metals oxide content is 5.0wt% ~ 30.0wt%, preferably 8.0wt% ~ 30.0wt%, group VIII metal oxide content is 0.5wt% ~ 15.0 wt%, preferably 2.0 wt% ~ 12.0 wt%.
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| CN107442161A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading and its preparation method and application |
| CN110038622A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation method |
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| CN110038622B (en) * | 2018-01-16 | 2021-12-07 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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