CN103100416B - Diesel oil hydro-upgrading catalyst and preparation method thereof - Google Patents
Diesel oil hydro-upgrading catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a diesel oil hydro-upgrading catalyst and a preparation method thereof. The catalyst comprises: a carrier composed of a modified beta molecular sieve and alumina, and hydrogenation active metal components. Specifically, the modified beta molecular sieve is prepared by: subjecting a crystallized beta molecular sieve slurry directly to ammonium exchange and a template agent removal treatment, then conducting a hydrothermal treatment first, and performing an aluminum salt solution treatment, under the condition of maintaining a high beta molecular sieve crystallinity, removing part of non-framework aluminum uniformly, thus obtaining the beta molecular sieve with the characteristics of high Si/Al ratio, large specific surface area, appropriate acidity and acid distribution, and reasonable pore structure, etc. The modified beta molecular sieve especially has a suitable cracking effect and a very good isomerization effect on long-chain alkane and the long side chain alkyl of aromatic hydrocarbon and cyclane, so that the catalyst can greatly reduce the condensation point of diesel oil fraction while keeping a high diesel oil yield, improve the cetane number of modified diesel oil, as well as effectively reduce the density and sulfur content of a diesel oil product.
Description
Technical field
The present invention relates to a kind of diesel oil hydrogenation modification Catalysts and its preparation method, particularly one can take poor ignition quality fuel as raw material, and the diesel oil of production has the diesel oil hydrogenation modification Catalysts and its preparation method that diesel product yield is high, Cetane number is high, density reduces the feature that amplitude is large and condensation point is low.
Background technology
Due to the advantage in Diesel engine performance and widely use, so always very vigorous to the demand of diesel oil.In addition, be the ecological environment that the protection mankind depend on for existence, higher requirement be it is also proposed to the quality of diesel product." world's fuel oil specification ", from II class standard, just proposes stricter requirement to indexs such as the sulphur in diesel oil and arene content, Cetane number, density, T95.
The diesel oil of current production mainly contains straight-run diesel oil and secondary processing diesel oil.The main path producing secondary processing diesel oil has catalytic cracking, hydrocracking and delayed coking.Due to the raising of clean fuel standards, cause catalytic diesel oil and coker gas oil can not meet index request, need process further to dispatch from the factory.How to use alap investment and operating cost, the fuel oil for vehicles of production environment close friend, become the problem that oil refining enterprise is urgently to be resolved hurrily.
Produce for clean diesel, prior art mainly comprises the technology such as hydrofinishing and MHUG.Hydrofinishing effectively can reduce the sulfur content of upgrading diesel oil, but limited to improving Cetane number and reducing T95 temperature capability.MHUG utilizes suitable for diesel oil cracking under the condition of middle pressure, the naphtha of generating portion and wide cut diesel fuel, and at present in the Y zeolite of the Cracking Component that adopts in pressure diesel modifying catalyst mainly modification, because Y zeolite has the supercage structure of twelve-ring, the shortcoming such as such that the amplitude that the dry gas amount amount of existing diesel modifying catalyst is large, the yield of diesel product is low, Cetane number improves is little, the recovery of T95 point is little, condensation point is high and density is large.Such as, CN1184843A and CN101463271A.CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, this catalyst consist of aluminium oxide 40 ~ 80wt%, amorphous silicon aluminium 0 ~ 20wt%, molecular sieve 5 ~ 30wt%, described molecular sieve is pore volume 0.4 ~ 0.52mL/g, specific area 750 ~ 900m
2/ g, lattice constant 2.420 ~ 2.500nm, silica alumina ratio is the Y zeolite of 7 ~ 15.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly adopt the predecessor of silica-alumina, aluminium oxide and/or aluminium oxide and Y zeolite mixing, shaping and roasting, introduce the hydrogenation metal of effective dose afterwards at shaping species.Above-mentioned catalyst has higher desulfurization and denitrification activity, but the shortcoming such as the amplitude that the yield of diesel product is low, the Cetane number of diesel oil improves is little, condensation point is high and density is large.
The core of diesel oil hydrogenation modification technology is catalyst, and the core of catalyst is molecular sieve, relative to Y zeolite, beta-molecular sieve has three-dimensional twelve-ring pore structure, but there is no the supercage structure as Y zeolite, its main feature is two 6 ring unit bug hole structures of two 4 rings and four 5 rings, main channel diameter is at 0.56-0.75nm, the duct feature of beta-molecular sieve makes it in cracking reaction, have good effect to the fracture of chain hydrocarbon-selective, and there is very strong isomery performance, Low Freezing Point diesel oil is can be used for as cracking component, reduce dry gas and naphtha makes.
CN1351121A discloses a kind of hydrocracking catalyst containing modified beta zeolite and amorphous aluminum silicide and preparation method thereof.Mentioning β Zeolite modifying method in the method is that β zeolite slurry after synthesis directly carries out ammonium salt exchange, and takes off ammonium, acid treatment and hydrothermal treatment consists through roasting and obtains modified β zeolite.In the method, first acid treatment is carried out to β zeolite, and then carry out hydrothermal treatment consists, adopt mineral acid treatment in acid treatment process, the skeleton structure of moieties sieve will be destroyed in this course, molecular sieve crystallinity declines, the non-skeleton structure forming bulk is stayed in molecular sieve pore passage, be difficult to be removed, affect acid distribution and the acid strength of modified molecular screen, in addition, also high-temperature water heat treatment has been carried out after acid treatment, also a certain amount of non-framework aluminum can be formed in molecular sieve, this will directly affect pore structure and the Acidity of molecular sieve, the acid distribution of molecular sieve and the change of Acidity using directly affect thus molecular sieve as the performance of the catalyst of Cracking Component, especially output and the product property of upgrading diesel oil is affected.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of diesel oil hydrogenation modification Catalysts and its preparation method.This catalyst for hydro-upgrading adopts a kind of high silica alumina ratio, bigger serface, acidity is suitable for, the rational beta-molecular sieve of pore structure does as predominant cracking component.The beta molecular sieve used can keep on the basis that skeleton is complete, even remove portion non-framework aluminum, is had the features such as diesel product yield height and good product quality by modifying catalyst of the present invention.
Diesel oil hydrogenation modification catalyst of the present invention, comprises the carrier and hydrogenation active metals component that are made up of modified beta molecular sieve and aluminium oxide; Wherein said modified beta molecular sieve, its character is as follows: specific surface 450m
2/ g ~ 750m
2/ g, is preferably 500 ~ 700m
2/ g, total pore volume 0.30mL/g ~ 0.45mL/g, SiO
2/ Al
2o
3mol ratio 40 ~ 100, preferably 50 ~ 80, relative crystallinity is 120% ~ 140%, and the mol ratio of meleic acid amount 0.1 ~ 0.5mmol/g, Gu Jia Lv ∕ non-framework aluminum is 5 ~ 20, B acid/L acid is 0.30 ~ 0.50, Na
2o≤0.15wt%, is preferably≤0.10wt%.
Described catalyst for hydro-upgrading carrier, with the weight of carrier for benchmark, the content of modified beta molecular sieve is 5% ~ 40%, and the content of aluminium oxide is 95% ~ 60%.
The specific area of catalyst for hydro-upgrading carrier of the present invention is 300 ~ 500m
2/ g, pore volume is 0.5 ~ 1.0mL/g.
Described hydrogenation active metals is the metal of group vib and group VIII, and group vib metal is preferably Mu He ∕ or tungsten, and the metal of group VIII is preferably Gu He ∕ or nickel.With the weight of catalyst for benchmark, the content of group vib metal (with oxide basis) is 10.0% ~ 30.0%, and the content of group VIII metal (with oxide basis) is 4.0% ~ 8.0%.
The preparation method of diesel oil hydrogenation modification catalyst of the present invention, comprising:
By modified beta molecular sieve, aluminium oxide, adhesive mechanical mixture, shaping, then dry and roasting, makes catalyst carrier; Adopt conventional method supported active metals in the catalyst carrier of gained;
Wherein said modified beta molecular sieve, comprises following preparation process:
(1) the beta-molecular sieve slurries after crystallization directly carry out ammonium exchange, filtration, washing, drying;
(2) dried beta-molecular sieve carries out Template removal process;
(3) beta-molecular sieve having taken off template carries out hydrothermal treatment consists again.
(4) with the beta molecular sieve of aluminum saline solution treatment step (3) gained, then filter, wash and drying.
In step (2), described Template removal process adopts conventional method to carry out, and general employing aerobic high-temperature process, in open kiln, process dried beta-molecular sieve, treatment temperature is 400 ~ 800 DEG C, and the processing time is 5 ~ 20 hours.
In step (3), described hydrothermal treatment consists operates in dedicated molecular sieve used hydrothermal treatment consists stove, and treatment conditions are: gauge pressure 0.05 ~ 0.4MPa, be preferably 0.1 ~ 0.2MPa, temperature 450 ~ 750 DEG C, be preferably 500 ~ 700 DEG C, 0.5 ~ 5 hour processing time, preferably 1 ~ 3 hour.
In step (4), in the solution of described aluminium salt, the concentration of aluminium salt is (with Al
3+meter) 0.1 ~ 2.0mol/L, preferably 0.5 ~ 1.5mol/L.It is formulated that the solution of described aluminium salt can adopt aluminium salt to be added to the water, and aluminium salt can be one or more in aluminum nitrate, aluminium chloride, aluminum sulfate.The solution of aluminium salt and the weight ratio of molecular sieve are 3:1 ~ 50:1.Described treatment conditions: temperature 40 ~ 120 DEG C, be preferably 70 ~ 100 DEG C, the time is 0.5 ~ 8.0 hour, preferably 1.0 ~ 3.0 hours.Described washing conditions: until cleaning solution pH value is close to neutrality, then under the condition of 100 ~ 120 DEG C dry 3 ~ 6 hours.
Catalyst of the present invention adopt the beta-molecular sieve of modification first to carry out hydrothermal treatment consists after de-ammonium, the method of rear employing aluminium Ficus caricaL carrys out modified beta molecular sieve, can under the condition keeping beta-molecular sieve high-crystallinity, evenly deviate from part non-framework aluminum, make molecular sieve have suitable acid distribution and pore structure.Aluminium Ficus caricaL is used to be under a kind of condition of relative mitigation, under the prerequisite of not saboteur's sieve skeleton frame can be ensured, the part non-framework aluminum removing will formed after hydrothermal treatment consists uniformly, improve the ratio of framework aluminum and non-framework aluminum in molecular sieve, improve the pore passage structure of molecular sieve, make its absorption being more conducive to reactant and product, reaction and diffusion.In addition, aluminium Ficus caricaL beta-molecular sieve is adopted, because the silica alumina ratio of beta-molecular sieve itself is higher, in processing procedure, also will a small amount of aluminium be had to move back in the skeleton structure of molecular sieve, stabilize the skeleton structure of molecular sieve, improve the degree of crystallinity of molecular sieve, improve the Acidity of modified molecular screen.The beta-molecular sieve of this modification has high silica alumina ratio, bigger serface, acidity and the feature such as acid distribution is suitable, pore structure is reasonable.The long side chain n-alkyl of the modified beta molecular sieve that the present invention selects to long chain alkane and aromatic hydrocarbons, cycloalkane has suitable splitting action and good isomerization, make catalyst can maintenance high diesel yield while, reduce the condensation point of diesel oil distillate by a relatively large margin, improve the Cetane number of upgrading diesel oil by a relatively large margin, density and the sulfur content of diesel product are effectively reduced.
When being used for hydro-upgrading of inferior diesel by catalyst for hydro-upgrading of the present invention, particularly middle press strip part (4 ~ 12MPa) and process poor ignition quality fuel (catalytic diesel oil and coker gas oil), there is very high catalytic activity and diesel yield, and the condensation point reduction amplitude of diesel oil distillate is large, improve the Cetane number of upgrading diesel oil by a relatively large margin, the density of diesel product is effectively reduced, and can meet refinery and increase operating flexibility, increases device disposal ability, increases the needs that high-quality produces diesel oil further.
Detailed description of the invention
In modifying catalyst of the present invention, aluminium oxide can adopt aluminium oxide used in conventional catalyst, as macroporous aluminium oxide and ∕ or little porous aluminum oxide.
In modifying catalyst of the present invention, aluminium oxide is macroporous aluminium oxide, pore volume 0.7 ~ 1.0mL/g, specific area 200 ~ 500m
2/ g.
Adhesive therefor of the present invention is made up of little porous aluminum oxide and inorganic acid and/or organic acid.Aperture aluminium oxide pore volume used is 0.3 ~ 0.5mL/g, and specific area is 200 ~ 400m
2/ g.
The beta-molecular sieve of modification in modifying catalyst of the present invention, concrete preparation method is as follows:
(1) the beta-molecular sieve slurries after crystallization directly carry out ammonium exchange, filtration, washing, drying
Beta-molecular sieve after above-mentioned crystallization is generally with organic ammonium (as tetraethyl ammonium hydroxide) for template, with hydrothermal crystallization method synthesis.Its chemical SiO
2/ Al
2o
3(mol ratio) is generally 20 ~ 30, Na
2the content of O is 3.0 ~ 4.0wt%.Beta-molecular sieve slurries after crystallization directly carry out ammonium salt exchange, and the concentration of ammonium salt in slurries is 0.5 ~ 5.0mol/L, and ammonium exchanges and carries out several, to make after exchange Na in molecular sieve
2o weight content is less than 0.3%, and general ammonium exchanges 1 ~ 5 time, can reach requirement.Beta-molecular sieve after ammonium salt exchanges carries out filtering, wash, dry;
(2) dried beta-molecular sieve carries out Template removal process
Template is with the addition of in the process of crystallization synthesis beta-molecular sieve, if this template is present in molecular sieve, will have a direct impact the catalyst taking beta-molecular sieve as Cracking Component, the duct of blocking beta-molecular sieve, and then forming the acid centre that carbon distribution occupies molecular sieve, the cracking performance affecting catalyst plays.Therefore need template to remove, the mode removing template generally adopts aerobic roasting, the beta-molecular sieve that namely treatment step (1) obtains in open kiln, and treatment temperature is 400 ~ 800 DEG C, and the processing time is 5 ~ 20 hours, controls carbon residue≤0.2 wt%;
(3) beta-molecular sieve having taken off template carries out hydrothermal treatment consists again
The molecular sieve obtained in hydrothermal treatment step (2) carries out in special hydrothermal treatment consists stove, hydrothermal conditions is: adopt 100wt% water vapour, at gauge pressure 0.05 ~ 0.4MPa, be preferably 0.1 ~ 0.2MPa, temperature 450 ~ 750 DEG C, be preferably 500 ~ 700 DEG C, 0.5 ~ 5.0 hour processing time, preferably 1.0 ~ 3.0 hours;
(4) with the beta-molecular sieve of solution treatment steps (3) gained of aluminium salt, then filter, wash and drying
Adding aluminum saline solution with return-flow system in airtight container, wherein aluminium salinity is (with Al
3+meter) 0.1 ~ 2.0mol/L, preferably 0.5 ~ 1.5mol/L, stirs and is warmed up to 40 ~ 120 DEG C, is preferably 70 ~ 100 DEG C, then be 3:1 ~ 50:1 by the weight ratio of aluminum salt solution and molecular sieve, add the molecular sieve that step (3) obtains, constant temperature stirs 0.5 ~ 8.0 hour, preferably 1.0 ~ 3.0 hours, filter, wash, washing, until cleaning solution pH value is close to neutrality, and under the condition of 100 ~ 120 DEG C dry 3 ~ 6 hours, obtains beta-molecular sieve of the present invention.Wherein the solution of aluminium salt can be one or more the aqueous solution in aluminium chloride, aluminum nitrate, aluminum sulfate.
Detailed process prepared by modifying catalyst of the present invention is:
Modified beta molecular sieve, aluminium oxide and adhesive are mixed, extruded moulding, then carries out drying and roasting, is prepared into carrier, and described drying can carry out 3 ~ 6 hours at the temperature of 80 DEG C to 150 DEG C, and roasting is 500 DEG C ~ 600 DEG C roastings 2.5 ~ 6 hours.
The load of catalyst activity metal of the present invention, carrying method conventional in prior art can be adopted, preferred infusion process, can be saturated leaching, excessive leaching or complexing leaching, namely with the solution impregnated catalyst carrier containing required active component, carrier after dipping, 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour, then 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 hours, obtains final catalyst.
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiments.
Analytical method of the present invention: specific surface and pore volume adopt low temperature liquid nitrogen physisorphtion, silica alumina ratio adopts chemical method, framework silicon-aluminum is adopted and is measured by NMR method, meleic acid amount, B acid amount and L acid amount adopt Pyridine adsorption IR spectra method, wherein the summation of B acid amount and L acid amount is meleic acid amount, sodium content adopts plasma emission spectrometry, and Electronic Speculum adopts projection Electronic Speculum, and relative crystallinity adopts XRD method to measure.In the present invention, wt% is mass fraction.
Embodiment 1
Modified beta molecular sieve of the present invention take tetraethyl ammonium hydroxide as template, adopts hydrothermal crystallization method to synthesize.Get commercial synthesis beta-molecular sieve former powder slurry 10000mL, be wherein about 2000g, its chemical sial SiO containing solid phase beta-molecular sieve
2/ Al
2o
3(mol ratio), than being 27.49, specific area is 101m2/g, and pore volume is 0.19cm3/g, and sodium oxide content is 3.67wt%.Add appropriate water purification in the slurry, and add a certain amount of ammonium nitrate, make liquid-solid ratio (weight) be 10:1, the concentration of ammonium nitrate is 2mol/L, stir, be warmed up to 95 ~ 100 DEG C, constant temperature stirs 2 hours, then filter, filter cake again secondary carries out ammonium exchange, and the condition of exchange is identical with first time, finally washs beta-molecular sieve to pH value neutrality, put into dry zone dry, drying 8 hours at 100 ~ 120 DEG C.Get dried beta-molecular sieve to carry out deviating from template process, adopt open kiln process, 570 DEG C of constant temperature process 15 hours.Gained molecular sieve label is B-1, and character is in table 1.
Embodiment 2
Getting 200g B-1 is raw material, carries out hydrothermal treatment consists to B-1, and at water vapor pressure 0.15MPa, treatment temperature is 550 DEG C, and the processing time is 2 hours.Gained molecular sieve is B-2, and character is in table 1.
Getting 200g B-1 is raw material, carries out hydrothermal treatment consists to B-1, and at water vapor pressure 0.15MPa, treatment temperature is 650 DEG C, and the processing time is 2 hours.Gained molecular sieve is B-3, and character is in table 1.
Embodiment 3
Take 60g B-2 molecular sieve to put into reflux and flask that can be airtight, add containing concentration 0.8mol/L aluminum sulfate aqueous solution 1000mL, at 95 DEG C, constant temperature stirs 1.0 hours, filters, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta molecular sieve of the present invention, its numbering B-4, molecular sieve character is in table 1.
Embodiment 4
Take 60g B-2 molecular sieve to put into reflux and flask that can be airtight, add containing concentration 0.4mol/L aluminum sulfate aqueous solution 1500mL, at 90 DEG C, constant temperature stirs 2 hours, filters, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven.Obtain beta molecular sieve of the present invention, its numbering B-5, molecular sieve character is in table 1.
Embodiment 5
Take 60g B-3 molecular sieve to put into reflux and flask that can be airtight, add containing concentration 0.6mol/L aluminum nitrate aqueous solution 2500mL, at 80 DEG C, constant temperature stirs 1.5 hours, filters, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta molecular sieve of the present invention, its numbering B-6, molecular sieve character is in table 1.
Embodiment 6
Take 60g B-3 molecular sieve to put into reflux and flask that can be airtight, add containing concentration 1.0mol/L alchlor aqueous solution 300mL, at 90 DEG C, constant temperature stirs 2.0 hours, filters, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta molecular sieve of the present invention, its numbering B-7, molecular sieve character is in table 1.
Comparative example 1
Get B-1 molecular sieve 300g, adopt the hydrochloric acid of 0.5mol/L to process, treatment conditions are: liquid-solid ratio 10:1, stir 2.5 hours at temperature 70 C constant temperature, filter, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping washing after 7, filter cake 120 DEG C of dryings 5 hours in an oven.By dried molecular sieve at water vapor pressure 0.15MPa, treatment temperature is 550 DEG C, and the processing time is 2 hours.Gained molecular sieve is B-8, and character is in table 1.
Comparative example 2
Get B-1 molecular sieve 300g, adopt the nitric acid of 0.7mol/L to process, treatment conditions are: liquid-solid ratio 10:1, stir 2.5 hours at temperature 80 DEG C of constant temperature, filter, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping washing after 7, filter cake 120 DEG C of dryings 5 hours in an oven.By dried molecular sieve at water vapor pressure 0.1MPa, treatment temperature is 600 DEG C, and the processing time is 2 hours.Gained molecular sieve is B-9, and character is in table 1.
Comparative example 3
Get B-1 molecular sieve 300g, adopt the sulfuric acid of 0.3mol/L to process, treatment conditions are: liquid-solid ratio 15:1, stir 2.5 hours at temperature 95 DEG C of constant temperature, filter, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping washing after 7, filter cake 120 DEG C of dryings 5 hours in an oven.By dried molecular sieve at water vapor pressure 0.2MPa, treatment temperature is 650 DEG C, and the processing time is 2 hours.Gained molecular sieve is B-10, and character is in table 1.
the character of table 1 embodiment and comparative example gained molecular sieve
| Embodiment 1 | Embodiment 2 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Numbering | B-1 | B-2 | B-3 | B-4 | B-5 |
| Silica alumina ratio | 27.80 | 27.80 | 27.80 | 59.9 | 63.4 |
| Specific area, m 2/g | 685 | 653 | 639 | 691 | 689 |
| Pore volume, mL/g | 0.389 | 0.403 | 0.416 | 0.421 | 0.426 |
| Relative crystallinity, % | 96 | 93 | 91 | 132 | 135 |
| Infrared acidity, mmol/g | 1.1 | 0.42 | 0.31 | 0.37 | 0.34 |
| Framework aluminum/non-framework aluminum | 18.5 | 11.6 | |||
| B acid/L acid | 0.45 | 0.38 | |||
| Na 2O，wt% | 0.23 | 0.23 | 0.23 | 0.03 | 0.02 |
table 1 continues
| Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Numbering | B-6 | B-7 | B-8 | B-9 | B-10 |
| Silica alumina ratio | 71.6 | 61.3 | 51.6 | 56.9 | 49.8 |
| Specific area, m 2/g | 677 | 647 | 621 | 632 | 643 |
| Pore volume, mL/g | 0.409 | 0.413 | 0.401 | 0.415 | 0.409 |
| Relative crystallinity, % | 131 | 138 | 123 | 120 | 125 |
| Infrared acidity, mmol/g | 0.26 | 0.27 | 0.35 | 0.30 | 0.25 |
| Framework aluminum/non-framework aluminum | 8.3 | 9.7 | 3.5 | 4.2 | 4.0 |
| B acid/L acid | 0.32 | 0.33 | 0.18 | 0.16 | 0.18 |
| Na 2O，wt% | 0.02 | 0.03 | 0.06 | 0.05 | 0.06 |
Embodiment 7
By 33.3 grams of B-5 molecular sieves (butt 90wt%), 200.0 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier FCS-1, character is in table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-1, and carrier and corresponding catalyst character are in table 2.
Embodiment 8
By 44.4 grams of B-5 molecular sieves (butt 90wt%), 171.4 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier FCS-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-2, and carrier and corresponding catalyst character are in table 2.
Embodiment 9
By 66.6 grams of B-6 molecular sieves (butt 90wt%), 142.9 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier FCS-3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-3, and carrier and corresponding catalyst character are in table 2.
Embodiment 10
By 77.8 grams of B-6 molecular sieves (butt 90wt%), 128.6 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier FCS-4.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-4, and carrier and corresponding catalyst character are in table 2.
Comparative example 4
By 44.4 grams of B-10 molecular sieves (butt 90wt%), 171.4 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier FCDS-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FCD-1, and carrier and corresponding catalyst character are in table 2.
Comparative example 5
By 66.6 grams of B-10 molecular sieves (butt 90wt%), 142.9 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier FCDS-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FCD-2, and carrier and corresponding catalyst character are in table 2.
Embodiment 11
This embodiment describes the catalyst activity evaluation result prepared by carrier of the present invention.Fixed bed hydrogenation experimental rig is evaluated, and appreciation condition is: reaction stagnation pressure 10.0MPa, hydrogen to oil volume ratio 800, volume space velocity 1.5h
-1, use catalytic diesel oil as feedstock oil, feedstock oil character lists in table 3.Catalyst FC-2, FCD-1 are evaluated under identical process conditions, the evaluation result obtained lists in table 4.
As can be seen from evaluation result, carrier prepared catalyst of the present invention is under identical process conditions, and diesel yield and product quality are all better than reference catalyst.
the physico-chemical property of table 2 catalyst carrier and catalyst
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 4 | Comparative example 5 | |
| Carrier composition and character | ||||||
| Numbering | FCS-1 | FCS-2 | FCS-3 | FCS-4 | FCDS-1 | FCDS-2 |
| Modified beta molecular sieve, wt% | 15 | 20 | 30 | 35 | 20 | 30 |
| Macroporous aluminium oxide, wt% | 70 | 60 | 50 | 45 | 60 | 50 |
| Adhesive, wt% | 20 | 20 | 20 | 20 | 20 | 20 |
| Pore volume, mL/g | 404 | 397 | 423 | 436 | 388 | 412 |
| Specific area, m 2/g | 0.73 | 0.65 | 0.60 | 0.57 | 0.66 | 0.61 |
| Catalyst composition and character | ||||||
| Numbering | FC-1 | FC-2 | FC-3 | FC-4 | FCD-1 | FCD-2 |
| WO 3，wt% | 18.7 | 24.8 | 23.4 | 21.6 | 24.3 | 22.9 |
| NiO，wt% | 5.5 | 6.3 | 5.9 | 6.2 | 6.5 | 6.0 |
table 3 feedstock oil character
| Feedstock oil | Catalytic diesel oil |
| Density (20 DEG C), g/cm 3 | 0.9423 |
| Boiling range, DEG C | |
| IBP/10% | 186/255 |
| 30%/50% | 286/310 |
| 70%/90% | 330/349 |
| 95%/EBP | 359/369 |
| Condensation point, DEG C | 5 |
| Sulphur, μ g/g | 8568 |
| Nitrogen, μ g/g | 1150 |
| Cetane number | 25 |
| C，wt% | 88.46 |
| H，wt% | 11.07 |
table 4 FC-2 and FCD-1 Evaluation results
| Catalyst | FC-2 | FCD-1 |
| Feedstock oil | Catalytic diesel oil | Catalytic diesel oil |
| Volume space velocity during liquid, h -1 | 1.5 | 1.5 |
| Reaction stagnation pressure, MPa | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 800:1 | 800:1 |
| Reaction temperature, DEG C | 370 | 375 |
| Product yield and character | ||
| Naphtha | ||
| Yield, wt% | 2.1 | 3.6 |
| Virtue is dived, wt% | 52.6 | 48.9 |
| Diesel oil | ||
| Yield, wt% | 96.6 | 93.5 |
| Density (20 DEG C), g/cm 3 | 0.8356 | 0.8372 |
| T95，℃ | 347 | 356 |
| Condensation point, DEG C | -22 | -13 |
| Cetane number | 49.6 | 44.7 |
| Sulphur, μ g/g | 6 | 15 |
| Liquid is received, wt% | 98.7 | 97.1 |
Claims (16)
1. a diesel oil hydrogenation modification catalyst, comprise the carrier and hydrogenation active metals component that are made up of modified beta molecular sieve and aluminium oxide, wherein said modified beta molecular sieve, its character is as follows: specific area 450m
2/ g ~ 750m
2/ g, total pore volume 0.30ml/g ~ 0.45ml/g, SiO
2/ Al
2o
3mol ratio 40 ~ 100, relative crystallinity is 120% ~ 140%, and the mol ratio of meleic acid amount 0.1 ~ 0.5mmol/g, Gu Jia Lv ∕ non-framework aluminum is 5 ~ 20, B acid/L acid is 0.30 ~ 0.50, Na
2o≤0.15wt%.
2., according to catalyst according to claim 1, it is characterized in that described beta-molecular sieve character is as follows: specific surface is 500 ~ 700m
2/ g.
3., according to the catalyst described in claim 1 or 2, it is characterized in that the SiO of described beta-molecular sieve
2/ Al
2o
3mol ratio 50 ~ 80.
4., according to catalyst according to claim 1, it is characterized in that described aluminium oxide is macroporous aluminium oxide, pore volume 0.7 ~ 1.0mL/g, specific area 200 ~ 500m
2/ g.
5. according to the catalyst described in claim 1 or 4, it is characterized in that described catalyst for hydro-upgrading carrier, with the weight of carrier for benchmark, the content of modified beta molecular sieve is 5% ~ 40%, and the content of aluminium oxide is 95% ~ 60%.
6., according to catalyst according to claim 1, it is characterized in that the specific area of described catalyst for hydro-upgrading carrier is 300 ~ 500m
2/ g, pore volume is 0.5 ~ 1.0mL/g.
7. according to catalyst according to claim 1, it is characterized in that described hydrogenation active metals is the metal of group vib and group VIII, group vib metal is Mu He ∕ or tungsten, and the metal of group VIII is Gu He ∕ or nickel; With the weight of catalyst for benchmark, group vib metal with the content of oxide basis for 10.0% ~ 30.0%, group VIII metal with the content of oxide basis for 4.0% ~ 8.0%.
8. the preparation method of the arbitrary described catalyst of claim 1 ~ 7, comprising:
By modified beta molecular sieve, aluminium oxide, adhesive mechanical mixture, shaping, then dry and roasting, makes catalyst carrier; Adopt conventional method supported active metals in the catalyst carrier of gained;
Wherein said modified beta molecular sieve, comprises following preparation process:
(1) the beta-molecular sieve slurries after crystallization directly carry out ammonium exchange, filtration, washing, drying;
(2) dried beta-molecular sieve carries out Template removal process;
(3) beta-molecular sieve having taken off template carries out hydrothermal treatment consists again;
(4) with the beta molecular sieve of solution treatment steps (3) gained of aluminium salt, then filter, wash and drying;
In step (3), described hydrothermal conditions is: gauge pressure 0.05 ~ 0.4MPa, temperature 450 ~ 750 DEG C, 0.5 ~ 5 hour processing time; In step (4), in the solution of described aluminium salt, the concentration of aluminium salt is with Al
3+count 0.1 ~ 2.0mol/L, the solution of aluminium salt and the weight ratio of molecular sieve are 3:1 ~ 50:1, described treatment conditions: temperature 40 ~ 120 DEG C, and the time is 0.5 ~ 8.0 hour.
9., according to preparation method according to claim 8, it is characterized in that in step (3), described hydrothermal conditions is: gauge pressure 0.1 ~ 0.2MPa, temperature is 500 ~ 700 DEG C, and the processing time is 1 ~ 3 hour.
10., according to preparation method according to claim 8, it is characterized in that, in step (4), in the solution of described aluminium salt, the concentration of aluminium salt is with Al
3+count 0.5 ~ 1.5mol/L.
11. according to preparation method according to claim 8, it is characterized in that the treatment conditions described in step (4): temperature is 70 ~ 100 DEG C, and the time is 1.0 ~ 3.0 hours.
12. according to preparation method according to claim 8, it is characterized in that described aluminium salt is one or more in aluminum nitrate, aluminium chloride, aluminum sulfate.
13. according to preparation method according to claim 8, it is characterized in that the drying condition described in step (4) is as follows: drying 3 ~ 6 hours under the condition of 100 ~ 120 DEG C.
14. according to preparation method according to claim 8, it is characterized in that in step (2), and described Template removal process adopts aerobic high-temperature process, and treatment temperature is 400 ~ 800 DEG C, and the processing time is 5 ~ 20 hours.
15., according to preparation method according to claim 8, is characterized in that, Na in beta-molecular sieve after step (1) ammonium exchanges
2o weight content is less than 0.3%.
16., according to preparation method according to claim 8, is characterized in that, after shaping, the condition that carrier carries out drying and roasting is as follows: 80 DEG C ~ 150 DEG C dryings 3 ~ 6 hours, 500 DEG C ~ 600 DEG C roastings 2.5 ~ 6.0 hours.
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| CN104667984B (en) * | 2013-11-26 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading carrier and preparation method thereof |
| CN104667967B (en) * | 2013-11-26 | 2017-04-12 | 中国石油化工股份有限公司 | Diesel hydroupgrading catalyst and preparation method thereof |
| CN104667955B (en) * | 2013-11-26 | 2017-05-17 | 中国石油化工股份有限公司 | A catalyst for hydrogenation modification and a preparing method thereof |
| CN106140253B (en) * | 2015-03-27 | 2018-10-12 | 中国石油化工股份有限公司 | Diesel oil hydrogenation modification catalyst and preparation method thereof |
| CN107344107B (en) * | 2016-05-05 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading and preparation method thereof |
| CN114477219B (en) * | 2020-10-27 | 2023-07-28 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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