CN106669863B - The method of modifying of catalyst for hydro-upgrading carrier - Google Patents
The method of modifying of catalyst for hydro-upgrading carrier Download PDFInfo
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Abstract
The invention discloses a kind of method of modifying of catalyst for hydro-upgrading carrier.This method comprises: the preparation of catalyst for hydro-upgrading carrier, sequentially or simultaneously introduces catalyst for hydro-upgrading carrier for water-soluble silicon oil and soluble zirconium-containing compound, after Overheating Treatment, modified catalyst for hydro-upgrading carrier is made.The modified support prepared through the method for the present invention is capable of providing more acid sites B, strong acid center is reduced, and the distribution of acid centre and hydrogenation sites can be adjusted, makes its mutually coordinated effect, the comprehensive performance of catalyst is improved, which is suitable for as diesel oil hydrogenation modification catalyst carrier.
Description
Technical field
The present invention relates to a kind of method of modifying of catalyst for hydro-upgrading carrier, especially urging for diesel oil hydrogenation modification
The method of modifying of agent carrier.
Background technique
For cleaning diesel production, the prior art mainly includes the technologies such as hydrofinishing and Medium Pressure Hydrogenation Modification.Add hydrogen smart
System can reduce the sulfur content of modification diesel oil, but limited to improvement Cetane number and reduction T95 temperature capability.Medium Pressure Hydrogenation Modification is
Using the catalyst for hydro-upgrading for containing molecular sieve (such as Y type molecular sieve, beta-molecular sieve), the aromatic hydrocarbons etc. in diesel oil is suitably cracked,
In reducing diesel oil while sulphur, nitrogen impurity content, improve the comprehensive performances such as diesel cetane-number.But hydrogen is added to change using current
Matter catalyst leads to improve the comprehensive performance (sulphur nitrogen impurity content, Cetane number, T95 temperature, arene content etc.) of diesel oil
Higher cracking degree is often needed, diesel yield can be made lower in this way, and to keep the yield of diesel oil, the comprehensive performance of diesel oil is again
It cannot improve well.
Sulfur-containing compound and aromatic hydrocarbons in diesel oil distillate usually exist with complicated structure, such as dibenzothiophenes, alkyl
Benzothiophene and methyldibenzothiophene etc., wherein plus the more difficult removing of hydrogen is dibenzothiophenes, alkyl benzothiophenes and alkyl
The thiophenes such as dibenzothiophenes, especially with 4,6- dimethyl Dibenzothiophene (4,6- BMDBT) and 2,4,6- front threes
Base dibenzothiophenes (2,4,6- BMDBT) class formation is complicated and has the sulfur-containing compound of space steric effect to be most difficult to remove.It reaches
To depth and ultra-deep desulfurization, it is necessary to remove these sulfur-containing compounds that structure is complicated and steric hindrance is big, and these sulfur-bearings
The compound usually more difficult removing under the hydrofinishing operating condition of the harshness such as high temperature and pressure can reduce bavin by being hydrocracked
Oil yield.Therefore, in the case where keeping the higher situation of diesel yield, the impurity in diesel oil how is removed, while diesel oil can be improved again
Comprehensive performance, this is the important topic for currently needing to study.
Catalyst for hydro-upgrading is usually to use the alumina support containing molecular sieve, currently, the side being modified to carrier
There are many method, wherein introducing auxiliary agent such as silicon, phosphorus, fluorine, boron, zirconium, titanium, magnesium, gallium, vanadium, manganese, copper, zinc etc., can be used to improve carrier
Property, but the dosage of auxiliary agent, type and mode are different due to introducing, and the property of alumina support can be made different or even difference
It is very big.CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, the group of the catalyst become 40~80wt% of aluminium oxide,
0~20wt% of amorphous silica-alumina, 5~30wt% of Y type molecular sieve.CN101463271A discloses a kind of hydro-upgrading of inferior diesel and urges
Agent and preparation method thereof, it is mainly mixed using silica-alumina, the predecessor of aluminium oxide and/or aluminium oxide and Y type molecular sieve
It closes, form and roasts, introduce a effective amount of hydrogenation metal in molding species later.Above-mentioned catalyst desulfurization with higher and de-
The disadvantages of nitrogen is active, but the amplitude that the yield of diesel product is low, the Cetane number of diesel oil improves is small, condensation point is high and density is big.
CN201110350790.2 discloses a kind of diesel oil hydrogenation modification catalyst and preparation method thereof.The catalyst includes
The carrier and hydrogenation active metal component be made of modified beta molecular sieve and aluminium oxide.Changed using the catalyst for diesel oil hydrogenation
When matter, although the condensation point of diesel oil distillate can be reduced, the Cetane number of modification diesel oil is improved, diesel yield is 97% hereinafter, still
It is so lower.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of modification sides of catalyst for hydro-upgrading carrier
Method.Carrier through the modified preparation of the method for the present invention is capable of providing more acid sites B, reduces strong acid center, and can adjust acid
Property center and hydrogenation sites distribution, make its mutually coordinated effect, improve the comprehensive performance of catalyst, the modified support is suitable
Preferably it is used as diesel oil hydrogenation modification catalyst carrier.
The method of modified catalyst for hydro-upgrading carrier provided by the invention, comprising: the system of catalyst for hydro-upgrading carrier
It is standby, water-soluble silicon oil and soluble zirconium-containing compound are sequentially or simultaneously introduced into catalyst for hydro-upgrading carrier, through Overheating Treatment
Afterwards, modified catalyst for hydro-upgrading carrier is made.
Catalyst for hydro-upgrading carrier of the present invention can carry for the catalyst for hydro-upgrading of conventional method preparation
Body can be free of adjuvant component, can also contain adjuvant component, wherein helping usually using aluminium oxide and molecular sieve as main component
Agent component can be one of fluorine, silicon, phosphorus, titanium, zirconium, boron etc. or a variety of, the content of adjuvant component in the carrier 15wt% with
Under, preferably 10wt% or less.Catalyst for hydro-upgrading carrier of the present invention can be using systems such as kneading method, mixing plastic methods
Standby, the general process of kneading method is as follows, by after aluminium hydroxide (such as boehmite) and molecular sieve mixed-forming by high temperature
Obtained after roasting, the condition of high-temperature roasting is as follows: 450 DEG C~1000 DEG C roastings 1.0h~20.0h, preferably 3.0 h ~
8.0 h.The general process for mixing plastic method is that molecular sieve is introduced during preparing alumine hydroxide colloid, after plastic, is made
Alumina dry glue containing molecular sieve is formed, and carrier is made, and wherein the condition of high-temperature roasting is as follows: 450 in dry and roasting
DEG C~1000 DEG C of roasting 1.0h~20.0h, the preferably h of 3.0 h ~ 8.0.The shape of carrier can according to need be made it is spherical,
Common shaping assistant can be added in forming process in the suitable shape such as bar shaped (such as clover, bunge bedstraw herb or cylindrical bars), than
Such as extrusion aid, peptization acid, adhesive.The property of the catalyst for hydro-upgrading carrier is as follows: specific surface area be 200 ~
550m2/ g, preferably 280 ~ 450m2/g；0.4 ~ 1.3mL/g of Kong Rongwei, preferably 0.6 ~ 1.0mL/g.
Molecular sieve of the present invention is Y type molecular sieve and/or beta-molecular sieve.With the weight of catalyst for hydro-upgrading carrier
On the basis of, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%, and preferably the content of molecular sieve is 3% ~ 20%,
The content of aluminium oxide is 80% ~ 97%.Wherein the molecular sieve is hydrogen type molecular sieve.Wherein beta-molecular sieve preferred property is as follows:
SiO2/Al2O3Molar ratio is 30 ~ 150, specific surface area 400m2/ g~750m2/ g, total pore volume 0.30mL/g~0.55mL/g are infrared
0.1~0.8mmol/g of acid amount；Y type molecular sieve preferred property is as follows: SiO2/Al2O3Molar ratio is 5 ~ 50, specific surface area 450m2/
G~800m2/ g, total pore volume 0.30mL/g~0.60mL/g, 0.2~0.9mmol/g of meleic acid amount.Beta-molecular sieve and Y type of the present invention
Existing method preparation can be used in molecular sieve.
In the method for the present invention, the silicone content being introduced into carrier by water-soluble silicon oil accounts for modified plus hydrogen in terms of silica
The 0.2%~7.0% of modifying catalyst vehicle weight, preferably 0.3%~4.0%, further preferably 0.5% ~ 1.8%.
In the method for the present invention, the zirconium content being introduced into carrier by soluble zirconium-containing compound is accounted for modified in terms of zirconium oxide
The 0.4%~10.0% of catalyst for hydro-upgrading vehicle weight, preferably 0.5%~5.0%, further preferably 0.5%~
2.5%.
In the method for the present invention, the dosage of water-soluble silicon oil and soluble zirconium-containing compound is introduced respectively with silica and oxidation
The molar ratio of zirconium meter is 0.04 ~ 36.0, preferably 0.12 ~ 16.0, more preferably 0.40 ~ 7.5.
Water-soluble silicon oil described in the method for the present invention refers to that the silicone oil that can be dissolved in water, preferred property are as follows: viscous at 25 DEG C
Degree is 200 ~ 7000mPa.s, and preferably 500 ~ 5000mPa.s, cloud point is 30 ~ 100 DEG C, preferably 40 ~ 65 DEG C.Described is water-soluble
What the method that group modified silicone oil is usually used in property silicone oil obtained, such as polyether modified silicon oil.
In the method for the present invention, soluble zirconium-containing compound refer to one of zirconium nitrate, zirconium chloride, zirconium oxychloride etc. or
Several combinations.
In the method for the present invention, water-soluble silicon oil and soluble zirconium-containing compound are sequentially or simultaneously introduced into hydro-upgrading catalysis
On agent carrier, first water-soluble silicon oil can be introduced on catalyst for hydro-upgrading carrier, then again by soluble chemical combination containing zirconium
Object is introduced on catalyst for hydro-upgrading carrier；Or water-soluble silicon oil and soluble zirconium-containing compound are introduced into add hydrogen simultaneously
On modifying catalyst carrier, incorporation way uses infusion process, and infusion process can be incipient impregnation, be also possible to excessive leaching
Stain；It can be multiple dipping, be also possible to single-steeping.To improve efficiency, an incipient impregnation is preferably used.
In the method for the present invention, using two sections of heat treatments, first segment is 60 DEG C~150 DEG C in temperature, excellent for the heat treatment
Be selected as 90 DEG C~120 DEG C, the processing time is 0.5h~20.0h, preferably 1.0h~6.0h, second segment temperature be 180 DEG C~
400 DEG C, preferably 200 DEG C~350 DEG C, the processing time is 0.5h~20.0h, preferably 1.0h~6.0h.Heat treatment can be
It is carried out in oxygen-containing atmosphere, oxygen concentration is not particularly limited, such as air atmosphere, can also carried out in an inert atmosphere, than
Such as nitrogen atmosphere.
Modification catalyst for hydro-upgrading carrier prepared by the method for the present invention, with a small amount of specific water-soluble silicon oil-impregnated
Catalyst for hydro-upgrading carrier makes it load to hydro-upgrading and is catalyzed using the effect of the hydrophilic and hydrophobic grouping of water-soluble silicon oil
On the specific position on agent carrier surface, and make while or the zirconium-containing compound that impregnates afterwards evenly spread to around siloxy group,
By suitable heat treatment, the better coordinative role of Si, Zr energy loaded forms more points in carrier surface specific position
On the one hand the uniform silicon zirconium hydroxyl of cloth makes carrier surface form more acid suitable acid centres, and with the original in carrier
Acidic site matches, and keeps the acidity of carrier and acid distribution more reasonable, reduces strong acid content, provide more acid sites B, separately
On the one hand, be conducive to adjust the distribution for the hydrogenation sites that the subsequent active metal using infusion process load is formed, Yi Jijia
The cooperation of the acid centre of hydrogen activity center and carrier, to improve the service performance of catalyst.
The modification catalyst for hydro-upgrading carrier of the method for the present invention preparation, is especially suitable as diesel oil hydrogenation modification catalyst
Carrier, the catalyst be used for diesel oil hydrogenation modification during, have deep hydrodesulfurizationof activity, and can keep diesel yield
Improve the comprehensive performances such as Cetane number in higher situation.
Specific embodiment
In the present invention, cloud point refers to be stopped after the water-soluble silicon oil solution for being 1% by mass concentration is heated to muddiness
Temperature when lower observation aqueous solution becomes limpid by muddiness is stirred in heating.
According to the method for modifying of catalyst for hydro-upgrading carrier provided by the invention, can specifically following steps be used:
1, soluble zirconium-containing compound is configured to solution A, wherein zirconium-containing compound concentration is calculated as 0.1g/ with zirconium oxide
100mL~32g/100mL；
2, water-soluble silicon oil is configured to solution B, wherein water-soluble silicon oil concentration with silica be calculated as 0.1g/100mL ~
20g/100mL；
3, soluble zirconium-containing compound and water-soluble silicon oil are hybridly prepared into solution C, wherein zirconium-containing compound concentration with
Zirconium oxide is calculated as 0.1g/100mL ~ 16g/100mL, and water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 10g/ with silica
100mL；
4, water-soluble silicon oil and zirconium-containing compound are guided to by catalyst for hydro-upgrading carrier using a kind of at least following mode
It is upper:
I, catalyst for hydro-upgrading carrier is impregnated with solution C, after health, then by two sections of heat treatments, obtained
Modified catalyst for hydro-upgrading carrier；Wherein in two sections of heat treatments, first segment is 60 DEG C~150 DEG C, preferably 90 DEG C in temperature
~120 DEG C, the processing time is 0.5h~20.0h, and preferably 1.0h~6.0h, second segment is 180 DEG C~400 DEG C in temperature, excellent
200 DEG C~350 DEG C are selected as, the processing time is 0.5h~20.0h, preferably 1.0h~6.0h；
II, it by Low Temperature Heat Treatment, then is impregnated after health with solution B dipping catalyst for hydro-upgrading carrier
Solution A after health, then by two sections of heat treatments, obtains modified catalyst for hydro-upgrading carrier；Wherein at Low Temperature Thermal
Reason is at 60 DEG C~150 DEG C, preferably 90 DEG C~120 DEG C, and the processing time is 0.5h~20.0h, preferably 1.0h~6.0h；Two
In section heat treatment, first segment is 60 DEG C~150 DEG C in temperature, and preferably 90 DEG C~120 DEG C, the processing time is 0.5h~20.0h,
Preferably 1.0h~6.0h, second segment are 180 DEG C~400 DEG C in temperature, and preferably 200 DEG C~350 DEG C, the processing time is 0.5h
~20.0h, preferably 1.0h~6.0h.
In the method for the present invention, heat treatment can carry out in oxygen-containing atmosphere, oxygen concentration be not particularly limited, such as air
Atmosphere etc. can also carry out in an inert atmosphere, such as nitrogen atmosphere etc..
The method of the present invention is not specifically limited the conditioned time after dipping solution, and conditioned time is can guarantee water-soluble silicon
Subject to oil and the uniform adsorption of zirconium-containing compound component, those skilled in the art can be according to the viscosity situation of solution and the suction of solution
Attached situation is judged, to determine conditioned time.
The technical solution that the invention is further illustrated by the following examples, but invention should not be deemed limited to this reality
It applies in example.In the present invention, wt% is mass fraction, and no specified otherwise is air atmosphere.
In the present invention, meleic acid amount, B acid and L acid are measured using Pyridine adsorption IR spectra method, and wherein meleic acid amount is B
The sum of acid and L acid acid amount.
In embodiment, water-soluble silicon oil A used is produced by Qingdao industrial organosilicon new material company, SiO2Content is
15wt%, viscosity (25 DEG C) 1500 ~ 5000 mPa.s, cloud point are 47 DEG C；Water-soluble silicon oil B is by Laiyang Shunming Chemical Co., Ltd
Production, SiO2Content is 9wt%, and (25 DEG C) of viscosity are 500~1500mPa.s, and cloud point is 45~55 DEG C；Water-soluble silicon oil C is by Lay
The production of Yang Shengbang organosilicon Science and Technology Ltd., SiO2Content is 30wt%, and (25 DEG C) of viscosity are 600~5000mPa.s, cloud point
It is 42~46 DEG C.
In embodiment, the property of beta-molecular sieve B1 used is as follows: SiO2/Al2O3Molar 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/Al2O3Molar 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 such as
Under: SiO2/Al2O3Molar ratio is 12, specific surface area 628m2/ g, total pore volume 0.48mL/g, meleic acid amount 0.49mmol/g；It is used
The property of Y type molecular sieve Y2 is as follows: SiO2/Al2O3Molar ratio is 25, specific surface area 640m2/ g, total pore volume 0.49mL/g are infrared
Acid amount 0.45mmol/g.
The diameter of cylindrical vector used is about 1.2mm in embodiment, and length is about 3 ~ 5mm, physico-chemical property such as 1 institute of table
Show.
The preparation of Z1: by beta-molecular sieve B1, macroporous aluminium oxide, (hole holds 1.0mL/g, specific surface area 400m2/ g), adhesive
(molar ratio of nitric acid and small porous aluminum oxide is 0.3) is put into mixed grind in roller, adds water, is rolled into paste, extrusion squeezes out item
It is 4 hours dry at 110 DEG C, it is then roasted 4 hours at 550 DEG C, obtains carrier Z1.
The preparation of Z2: by beta-molecular sieve B1, Y type molecular sieve Y1, macroporous aluminium oxide, (hole holds 1.0mL/g, specific surface area
400m2/ g), adhesive (molar ratio of nitric acid and small porous aluminum oxide is 0.3) be put into mixed grind in roller, add water, be rolled into paste
Cream, extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier Z2.
The preparation of Z3: by beta-molecular sieve B2, Y type molecular sieve Y2, macroporous aluminium oxide, (hole holds 1.0mL/g, specific surface area
400m2/ g), adhesive (molar ratio of nitric acid and small porous aluminum oxide is 0.3) be put into mixed grind in roller, add water, be rolled into paste
Cream, extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier Z3.
The physico-chemical property of catalyst for hydro-upgrading carrier used in 1 embodiment of table
| Project | Z1 | Z2 | Z3 |
| Beta-molecular sieve content, wt% | _ | 4 | 6 |
| Y molecular sieve content, wt% | 10 | 6 | 6 |
| Aluminium oxide | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 350 | 341 | 362 |
| Kong Rong, mL/g | 0.63 | 0.64 | 0.64 |
| It is saturated liquid absorption amount, mL/100g | 72 | 73 | 73 |
Mo predecessor in the present embodiment in Mo, Ni, P maceration extract used is MoO3, Ni predecessor is basic nickel carbonate, P
Predecessor is phosphoric acid.
Embodiment 1
Zirconium nitrate 18.6g is weighed, appropriate amount of deionized water dissolution is added, makes volume 105mL, obtained solution A1.Weigh water
Dissolubility silicone oil A 21.0g is added appropriate amount of deionized water dissolution, makes volume 105mL, obtained solution B1.It, will under stirring
35mL B1 solution is poured slowly into 35mL A1 solution, and appropriate amount of deionized water is added, and is made final volume 72mL, is configured to C1
Solution.
100g catalyst for hydro-upgrading carrier Z1 is taken, solution C 1 is uniformly sprayed on catalyst for hydro-upgrading carrier Z1,
After health 10 hours, modified carrier S 1 is obtained through 100 DEG C of heat treatments 2h, 230 DEG C of heat treatment 2h.
100g catalyst for hydro-upgrading carrier Z1 is taken, 35mL solution B 1 is diluted to 72mL with deionized water, is uniformly sprayed
On carrier Z1, health 10 hours, it is diluted to 71mL with deionized water after 100 DEG C of heat treatment 2h, then by 35mL A1 solution,
Uniformly sprinkling on this carrier, after health 3 hours, obtains modified carrier through 100 DEG C of heat treatments 2h, 230 DEG C of heat treatment 2h
S2。
Embodiment 2
Zirconium oxychloride 13.0g, water-soluble silicon oil B 36.0g are weighed, appropriate amount of deionized water dissolution is added, makes volume
146mL, obtained solution C2.
100g catalyst for hydro-upgrading carrier Z1 is taken, 73mL solution C 2 is uniformly sprayed at catalyst for hydro-upgrading carrier Z1
On, after health 10 hours, modified carrier S 3 is obtained through 100 DEG C of heat treatments 2h, 230 DEG C of heat treatment 2h.
100g catalyst for hydro-upgrading carrier Z1 is taken, 73mL solution C 2 is uniformly sprayed at catalyst for hydro-upgrading carrier Z1
On, after health 10 hours, in a nitrogen atmosphere, modified carrier is obtained through 100 DEG C of heat treatments 2h, 350 DEG C of heat treatment 2h
S4。
Embodiment 3
Zirconium nitrate 3.6g, water-soluble silicon oil C 2.7g are weighed, appropriate amount of deionized water dissolution is added, makes volume 73mL, makes
Obtain solution C 3.
100g catalyst for hydro-upgrading carrier Z2 is taken, solution C 3 is uniformly sprayed on catalyst for hydro-upgrading carrier Z2,
After health 10 hours, modified carrier S 5 is obtained through 100 DEG C of heat treatments 2h, 260 DEG C of heat treatment 2h.
Embodiment 4
Zirconium nitrate 16.5g, 12.5 g of water-soluble silicon oil C are weighed, appropriate amount of deionized water dissolution is added, makes volume 73mL,
Obtained solution C4.
100g catalyst for hydro-upgrading carrier Z2 is taken, solution C 4 is uniformly sprayed on catalyst for hydro-upgrading carrier Z2,
After health 10 hours, modified carrier S 6 is obtained through 100 DEG C of heat treatments 2h, 260 DEG C of heat treatment 2h.
Embodiment 5
Zirconium nitrate 7.2g, water-soluble silicon oil C 2.7g are weighed, appropriate amount of deionized water dissolution is added, makes volume 73mL, makes
Obtain solution C 5.
100g catalyst for hydro-upgrading carrier Z3 is taken, solution C 3 is uniformly sprayed on catalyst for hydro-upgrading carrier Z3,
After health 10 hours, modified carrier S 7 is obtained through 100 DEG C of heat treatments 2h, 260 DEG C of heat treatment 2h.
Comparative example 1
Water-soluble silicon oil A 7.0g is weighed, appropriate amount of deionized water dissolution is added, makes volume 72mL, obtained solution B2.It takes
100g catalyst for hydro-upgrading carrier Z1, solution B 2 is uniformly sprayed on catalyst for hydro-upgrading carrier Z1, and health 10 hours
Afterwards, modified carrier DS1 is obtained through 100 DEG C of heat treatments 2h, 230 DEG C of heat treatment 2h.
Comparative example 2
Zirconium nitrate 6.2g is weighed, appropriate amount of deionized water dissolution is added, makes volume 72mL, is configured to A2 solution.Take 100g
Solution A 2 is uniformly sprayed on catalyst for hydro-upgrading carrier Z1 by catalyst for hydro-upgrading carrier Z1, after health 10 hours, warp
100 DEG C of heat treatments 2h, 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, introduces water-soluble silicon afterwards
Oil, detailed process is as follows:
100g catalyst for hydro-upgrading carrier Z1 is taken, 35mL A1 solution is diluted to 72mL with deionized water, is uniformly sprayed
On this carrier, after health 3 hours, it is diluted to 71mL with deionized water through 100 DEG C of heat treatment 2h, then by 35mL solution B 1,
Even to be sprayed on carrier Z1, health 10 hours, after 100 DEG C of heat treatment 2h, 230 DEG C of heat treatment 2h obtained modified carrier
DS3。
2 embodiment of table and comparative example modified catalyst for hydro-upgrading carrier property
| 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 | 292 | 312 | 279 | 311 |
| Kong Rong, 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 acid, mmol/g | 0.122 | 0.119 | 0.125 | 0.131 | 0.118 | 0.110 | 0.119 |
| L acid, 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, which refers to, accounts for total acid content using acid amount when determination of infrared spectroscopy acid amount greater than 450 DEG C
Percentage.
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 |
| Kong Rong, 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 acid, mmol/g | 0.075 | 0.078 | 0.076 | 0.080 | 0.061 | 0.071 |
| L acid, 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 S7 in the embodiment of the present invention are taken respectively, are distinguished with Mo, Ni, P solution
After incipient impregnation 2h, 120 DEG C of dry 3h, 480 DEG C of roasting 2h respectively obtain catalyst T1, T2, T3, T4, T5, T6 and T7.
Comparative example 4 ~ 8
Take respectively comparative example of the present invention carrier strip DS1, DS2 and DS3 and embodiment used in carrier Z1 and Z2,
With Mo, Ni, P solution distinguish incipient impregnation 2h after, 120 DEG C of dry 3h, 480 DEG C of roasting 2h, respectively obtain catalyst DT1,
DT2, DT3, DT4 and DT5.
The composition of 3 catalyst of table
| Catalyst composition | 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 composition | 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 carries out on 100mL small hydrogenation device, carries out before performance evaluation to catalyst pre-
Vulcanization.Evaluating catalyst condition is 1.5 h of volume space velocity in reaction stagnation pressure 10.0MPa, liquid-1, hydrogen to oil volume ratio 800:1, instead
Answering temperature is 365 DEG C.Henchnmrk test is shown in Table 4 with raw material oil nature, and Evaluation results are shown in Table 5, by data in table as it can be seen that
The catalyst for hydro-upgrading prepared with method of modifying of the present invention, the desulphurizing activated of catalyst are apparently higher than comparative example catalyst,
The Cetane number of diesel oil is improved into 10 units or more under conditions of keeping diesel yield to be not less than 98%, product quality obtains
Improve well.
4 raw material oil nature of table
| 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 | 27 |
| C, wt% | 87.63 |
| H, wt% | 11.05 |
5 catalyst performance evaluation result of table
| Catalyst number | 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 number | 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 (27)
1. a kind of method of modifying of catalyst for hydro-upgrading carrier, comprising: the preparation of catalyst for hydro-upgrading carrier, it will be water-soluble
Silicone oil and soluble zirconium-containing compound sequentially or simultaneously introduce catalyst for hydro-upgrading carrier, after Overheating Treatment, are made and are modified
Catalyst for hydro-upgrading carrier afterwards；
Wherein, water-soluble silicon oil and soluble zirconium-containing compound are sequentially or simultaneously introduced to the introducing of catalyst for hydro-upgrading carrier
Mode uses infusion process；
Wherein, the catalyst for hydro-upgrading carrier is using aluminium oxide and molecular sieve as main component, with or without auxiliary agent
Component, wherein adjuvant component is one of fluorine, silicon, phosphorus, titanium, zirconium, boron or a variety of, and adjuvant component is based on the element in the carrier
Content is in 15wt% or less；
Wherein, the silicone content being introduced into carrier by water-soluble silicon oil accounts for modified catalyst for hydro-upgrading carrier in terms of silica
The 0.5% ~ 1.8% of weight；The zirconium content being introduced into carrier by soluble zirconium-containing compound is accounted for modified back end hydrogenation in terms of zirconium oxide and changed
The 0.4%~10.0% of matter catalyst carrier weight.
2. according to the method for claim 1, it is characterised in that: the property of the catalyst for hydro-upgrading carrier is as follows: ratio
Surface area is 200 ~ 550m20.4 ~ 1.3mL/g of/g, Kong Rongwei.
3. according to the method for claim 1, it is characterised in that: the property of the catalyst for hydro-upgrading carrier is as follows: ratio
Surface area is 280 ~ 450m20.6 ~ 1.0mL/g of/g, Kong Rongwei.
4. according to the method for claim 1, it is characterised in that: the catalyst for hydro-upgrading carrier using kneading method or
Mix the preparation of plastic method.
5. according to method described in claim 1 or 4, it is characterised in that: the catalyst for hydro-upgrading carrier is through forming
And the catalyst for hydro-upgrading carrier Jing Guo high-temperature roasting, the condition of high-temperature roasting are as follows: in 450 DEG C~1000 DEG C roasting 1.0h
~20.0h.
6. according to the method for claim 1, it is characterised in that: on the basis of the weight of catalyst for hydro-upgrading carrier, point
The content of son sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.
7. according to the method for claim 1, it is characterised in that: on the basis of the weight of catalyst for hydro-upgrading carrier, point
The content of son sieve is 3% ~ 20%, and the content of aluminium oxide is 80% ~ 97%.
8. according to method described in claim 1 or 6, it is characterised in that: the molecular sieve is Y type molecular sieve and/or beta molecule
Sieve.
9. according to the method for claim 8, it is characterised in that: the molecular sieve is hydrogen type molecular sieve, wherein beta-molecular sieve
Property is as follows: SiO2/Al2O3Molar ratio is 30 ~ 150, specific surface area 400m2/ g~750m2/ g, total pore volume 0.30mL/g~
0.55mL/g, 0.1~0.8mmol/g of meleic acid amount；Y type molecular sieve property is as follows: SiO2/Al2O3Molar ratio is 5 ~ 50, compares table
Area 450m2/ g~800m2/ g, total pore volume 0.30mL/g~0.60mL/g, 0.2~0.9mmol/g of meleic acid amount.
10. according to the method for claim 1, it is characterised in that: contained by the zirconium that soluble zirconium-containing compound is introduced into carrier
Amount accounts for the 0.5%~5.0% of modified catalyst for hydro-upgrading vehicle weight in terms of zirconium oxide.
11. according to the method for claim 1, it is characterised in that: contained by the zirconium that soluble zirconium-containing compound is introduced into carrier
Amount accounts for the 0.5%~2.5% of modified catalyst for hydro-upgrading vehicle weight in terms of zirconium oxide.
12. according to the method for claim 1, it is characterised in that: introduce water-soluble silicon oil and soluble zirconium-containing compound
The molar ratio in terms of silica and zirconium oxide is 0.04 ~ 36.0 to dosage respectively.
13. according to the method for claim 1, it is characterised in that: introduce water-soluble silicon oil and soluble zirconium-containing compound
The molar ratio in terms of silica and zirconium oxide is 0.12 ~ 16.0 to dosage respectively.
14. according to the method for claim 1, it is characterised in that: introduce water-soluble silicon oil and soluble zirconium-containing compound
The molar ratio in terms of silica and zirconium oxide is 0.40 ~ 7.5 to dosage respectively.
15. according to the method for claim 1, it is characterised in that: the property of the water-soluble silicon oil is as follows: at 25 DEG C
Viscosity is 200 ~ 7000mPa s, and cloud point is 30 ~ 100 DEG C.
16. according to the method for claim 1, it is characterised in that: the property of the water-soluble silicon oil is as follows: at 25 DEG C
Viscosity is 500 ~ 5000mPa s, and cloud point is 40 ~ 65 DEG C.
17. according to method described in claim 1 or 15, it is characterised in that: the water-soluble silicon oil is polyether modified silicon oil.
18. according to the method for claim 1, it is characterised in that: the soluble zirconium-containing compound is zirconium nitrate, tetrachloro
Change one or more of zirconium, zirconium oxychloride.
19. according to the method for claim 1, it is characterised in that: the heat treatment is existed using two sections of heat treatments, first segment
Temperature be 60 DEG C~150 DEG C, the processing time be 0.5h~20.0h, second segment temperature be 180 DEG C~400 DEG C, handle the time be
0.5h~20.0h.
20. according to the method for claim 1, it is characterised in that: the heat treatment is existed using two sections of heat treatments, first segment
Temperature be 90 DEG C~120 DEG C, the processing time be 1.0h~6.0h, second segment temperature be 200 DEG C~350 DEG C, handle the time be
1.0h~6.0h.
21. according to the method for claim 1, it is characterised in that: water-soluble silicon oil and soluble zirconium-containing compound successively draw
Enter onto carrier, incorporation way uses infusion process, i.e., first water-soluble silicon oil is impregnated on carrier, after health, by low
Soluble zirconium-containing compound, is then impregnated on carrier by warm processing again, is heat-treated by two sections, obtains modified plus hydrogen
Modifying catalyst carrier；Wherein Low Temperature Heat Treatment is at 60 DEG C~150 DEG C, and the processing time is 0.5h~20.0h.
22. according to the method for claim 21, it is characterised in that: the dipping solution for being made into soluble zirconium-containing compound
In, zirconium-containing compound concentration is calculated as 0.1g/100mL ~ 32g/100mL with zirconium oxide；The dipping solution that water-soluble silicon oil is made into
In, water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/100mL with silica.
23. according to the method for claim 1, it is characterised in that: water-soluble silicon oil and soluble zirconium-containing compound draw simultaneously
Enter onto carrier, incorporation way uses infusion process, i.e., water-soluble silicon oil and soluble zirconium-containing compound is impregnated into load simultaneously
On body, after health, it is heat-treated by two sections, obtains modified catalyst for hydro-upgrading carrier.
24. according to the method for claim 23, it is characterised in that: mix soluble zirconium-containing compound and water-soluble silicon oil
In the dipping solution of preparation, zirconium-containing compound concentration is calculated as 0.1g/100mL ~ 16g/100mL with zirconium oxide, and water-soluble silicon oil is dense
Degree is calculated as 0.1g/100mL ~ 10g/100mL with silica.
25. according to any method of claim 21 ~ 24, it is characterised in that: infusion process uses an incipient impregnation.
26. according to any method of claim 21 ~ 24, it is characterised in that: two sections of heat treatments, first segment is in temperature
Degree be 60 DEG C~150 DEG C, the processing time be 0.5h~20.0h, second segment temperature be 180 DEG C~400 DEG C, handle the time be
0.5h~20.0h.
27. according to any method of claim 21 ~ 24, it is characterised in that: two sections of heat treatments, first segment is in temperature
Degree be 90 DEG C~120 DEG C, the processing time be 1.0h~6.0h, second segment temperature be 200 DEG C~350 DEG C, handle the time be
1.0h~6.0h.
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| CN1772846A (en) * | 2005-11-17 | 2006-05-17 | 中国石油化工集团公司 | Coal tar hydrogenating modification catalyst and its prepn and application |
| CN101491767A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
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